Water-soluble polyvinyl alcohol blend film, related methods, and related articles

ABSTRACT

Disclosed herein are water-soluble films including a polyvinyl alcohol (PVOH) resin blend and optionally one or more additional components such as plasticizers, fillers, surfactants, and other additives. Also disclosed herein are articles including the water-soluble film and containing a composition such as a household care composition. The PVOH resin blend includes a PVOH copolymer including one or more types of anionic monomer units such as a PVOH terpolymer and a PVOH polymer such as a partially or completely hydrolyzed PVOH homopolymer. When the PVOH copolymer and PVOH polymer are blended in particular proportions and/or selected with regard to various criteria related to the 4% solution viscosity of one or both of the PVOH polymer(s) and PVOH copolymer(s), the resulting water-soluble film formed from the PVOH resin blend exhibits substantially improved aqueous dissolution properties.

FIELD OF THE DISCLOSURE

The disclosure relates generally to water-soluble films which include ablend of polyvinyl alcohol (PVOH) resins and which can be used forcontact with liquids, solids, or combinations thereof, for examplehousehold care compositions. The disclosure further relates to methodsof making the films as well as articles such as packets and pouches madefrom the films, which are optionally filled with active components,e.g., detergents, to make measured dose pouches. More particularly, thedisclosure relates to such films, packets, and pouches with one or morebenefits such as improved solubility characteristics for end uses and/orresistance to change in solubility characteristics upon contact withchemicals, together with suitable processability.

BACKGROUND

Water-soluble polymeric films are commonly used as packaging materialsto simplify dispersing, pouring, dissolving and dosing of a material tobe delivered. For example, packets made from water-soluble film arecommonly used to package household care compositions, e.g., a pouchcontaining a laundry or dish detergent. A consumer can directly add thepouch to a mixing vessel, such as a bucket, sink or washing machine.Advantageously, this provides for accurate dosing while eliminating theneed for the consumer to measure the composition. The pouch may alsoreduce mess that would be associated with dispensing a similarcomposition from a vessel, such as pouring a liquid laundry detergentfrom a bottle. The pouch also insulates the composition therein fromcontact with the user's hands. In sum, soluble polymeric film packetscontaining pre-measured agents provide for convenience of consumer usein a variety of applications.

Some water-soluble polymeric films that are used to make packets willincompletely dissolve during a wash cycle, leaving film residue on itemswithin the wash. Such problems may particularly arise when the pouch isused under stressed wash conditions, such as when the pouch is used incold water (e.g., water as low as 5° C. and/or up to 10° C. or 15° C.),in a short wash cycle, and/or in a low-water wash cycle (e.g., washliquors from about 3 L to about 20 L). Notably, environmental concernsand energy cost are driving consumer desire for utilizing colder washwater and shorter wash cycles.

There remains a need for water-soluble films and related articles suchas packets having the desired characteristics of good water solubility(e.g., cold water solubility), chemical resistance, chemical andphysical compatibility with laundry actives or other compositions incontact with the film or pouch formed therefrom, and desirablemechanical properties including good processability.

SUMMARY

The present disclosure relates a water-soluble film (e.g., which can beused to form articles such as pouches or packets, for example includinga household care composition proximal thereto) including a polyvinylalcohol (PVOH) resin blend and optionally one or more additionalcomponents such as plasticizers, fillers, surfactants, and otheradditives. The PVOH resin blend includes a PVOH copolymer including oneor more types of anionic monomer units (e.g., a PVOH terpolymer) and aPVOH polymer (e.g., a partially or completely hydrolyzed PVOHhomopolymer). When the PVOH copolymer and polymer are blended inparticular proportions and/or selected with regard to various criteriarelated to the 4% solution viscosity of one or both of the PVOH(co)polymers, the resulting water-soluble film formed from the PVOHresin blend exhibits beneficial aqueous dissolution properties(optionally in combination with beneficial tensile strength properties,and/or tensile modulus properties) relative to both (i) comparable filmsformed from single PVOH anionic copolymers and (ii) comparable filmsformed from PVOH copolymer and polymer blends outside the selectedproportions and/or the solution viscosity criteria. Optionally, theresulting water-soluble film formed from the PVOH resin blend furtherexhibits beneficial aqueous dissolution properties (optionally incombination with beneficial tensile strength properties, and/or tensilemodulus properties) relative to comparable films formed from PVOHpolymer blends without anionic monomer units (e.g., blends of partiallyor completely hydrolyzed PVOH homopolymers). Reduction or elimination ofaqueous dissolution residue is particularly desirable in various washingoperations, for example when a pouch formed from the water-soluble filmand containing a cleaning composition (e.g., a laundry or dishwashingcleaning composition) is used to clean one or more articles (e.g.,laundry or dishware), insofar as it is desirable for the cleanedarticles to be free from polymeric film residue.

One aspect of the disclosure relates to a water-soluble film including:a polyvinyl alcohol (PVOH) resin blend including: a first PVOH copolymerincluding an anionic monomer unit, the first PVOH copolymer having afirst 4% solution viscosity at 20° C. (μ₁); and a second PVOH polymerconsisting essentially of vinyl alcohol monomer units and optionallyvinyl acetate monomer units, the second PVOH polymer having a second 4%solution viscosity at 20° C. (μ₂); wherein: an absolute viscositydifference |μ₂−μ₁| for the first PVOH copolymer and the second PVOHpolymer is in a range of 0 cP to about 10 cP, and the first PVOHcopolymer is present in an amount in a range of about 30 wt. % to about90 wt. % of total PVOH polymers and PVOH copolymers in the film.

Another aspect of the disclosure relates to a water-soluble filmincluding: a polyvinyl alcohol (PVOH) resin blend including: a firstPVOH copolymer including an anionic monomer unit, the first PVOHcopolymer having a first 4% solution viscosity at 20° C. (μ₁); and asecond PVOH polymer consisting essentially of vinyl alcohol monomerunits and optionally vinyl acetate monomer units, the second PVOHpolymer having a second 4% solution viscosity at 20° C. (μ₂); wherein:an absolute viscosity difference |μ₂−μ₁| for the first PVOH copolymerand the second PVOH polymer is in a range of 0 cP to about 10 cP, andthe anionic monomer unit is present in the film in an amount in a rangeof about 1.0 mol. % to about 4.2 mol. % of total PVOH polymers and PVOHcopolymers in the film.

Another aspect of the disclosure relates to a water-soluble filmincluding: a polyvinyl alcohol (PVOH) resin blend including: a firstPVOH copolymer including an anionic monomer unit, the first PVOHcopolymer having a first 4% solution viscosity at 20° C. (μ₁); and asecond PVOH polymer consisting essentially of vinyl alcohol monomerunits and optionally vinyl acetate monomer units, the second PVOHpolymer having a second 4% solution viscosity at 20° C. (μ₂) of about 20cP or less; wherein: the first PVOH copolymer is present in an amount ina range of about 30 wt. % to about 90 wt. % of total PVOH polymers andcopolymers in the film.

Another aspect of the disclosure relates to a water-soluble filmincluding: a polyvinyl alcohol (PVOH) resin blend including: a firstPVOH copolymer including an anionic monomer unit, the first PVOHcopolymer having a first 4% solution viscosity at 20° C. (μ₁); and asecond PVOH polymer consisting essentially of vinyl alcohol monomerunits and optionally vinyl acetate monomer units, the second PVOHpolymer having a second 4% solution viscosity at 20° C. (μ₂) of about 20cP or less; wherein: the anionic monomer unit is present in the film inan amount in a range of about 1.0 mol. % to about 4.2 mol. % of totalPVOH polymers and PVOH copolymers in the film.

Another aspect of the disclosure relates to a water-soluble filmincluding: a polyvinyl alcohol (PVOH) resin blend including: a firstPVOH copolymer comprising a first anionic monomer unit; and a secondPVOH polymer consisting essentially of vinyl alcohol monomer units andoptionally vinyl acetate monomer units; wherein the first PVOH copolymeris present in an amount in a range of about 30 wt. % to about 70 wt. %of total PVOH polymers and PVOH copolymers in the film.

Another aspect of the disclosure relates to an article including awater-soluble film and a household care composition proximal to thefilm, where the film includes: a polyvinyl alcohol (PVOH) resin blendincluding: a first PVOH copolymer including an anionic monomer unit, thefirst PVOH copolymer having a first 4% solution viscosity at 20° C.(μ₁); and a second PVOH polymer consisting essentially of vinyl alcoholmonomer units and optionally vinyl acetate monomer units, the secondPVOH polymer having a second 4% solution viscosity at 20° C. (μ₂);wherein: an absolute viscosity difference |μ₂−μ₁| for the first PVOHcopolymer and the second PVOH polymer is in a range of 0 cP to about 10cP, and the first PVOH copolymer is present in an amount in a range ofabout 30 wt. % to about 90 wt. % of total PVOH polymers and PVOHcopolymers in the film.

Another aspect of the disclosure relates to an article including awater-soluble film and a household care composition proximal to thefilm, where the film includes: a polyvinyl alcohol (PVOH) resin blendincluding: a first PVOH copolymer including an anionic monomer unit, thefirst PVOH copolymer having a first 4% solution viscosity at 20° C.(μ₁); and a second PVOH polymer consisting essentially of vinyl alcoholmonomer units and optionally vinyl acetate monomer units, the secondPVOH polymer having a second 4% solution viscosity at 20° C. (μ₂);wherein: an absolute viscosity difference |μ₂−μ₁| for the first PVOHcopolymer and the second PVOH polymer is in a range of 0 cP to about 10cP, and the anionic monomer unit is present in the film in an amount ina range of about 1.0 mol. % to about 4.2 mol. % of total PVOH polymersand PVOH copolymers in the film.

Another aspect of the disclosure relates to an article including awater-soluble film and a household care composition proximal to thefilm, where the film includes: a polyvinyl alcohol (PVOH) resin blendincluding: a first PVOH copolymer including an anionic monomer unit, thefirst PVOH copolymer having a first 4% solution viscosity at 20° C.(μ₁); and a second PVOH polymer consisting essentially of vinyl alcoholmonomer units and optionally vinyl acetate monomer units, the secondPVOH polymer having a second 4% solution viscosity at 20° C. (μ₂) ofabout 20 cP or less; wherein: the first PVOH copolymer is present in anamount in a range of about 30 wt. % to about 90 wt. % of total PVOHpolymers and copolymers in the film.

Another aspect of the disclosure relates to an article including awater-soluble film and a household care composition, where the filmincludes: a polyvinyl alcohol (PVOH) resin blend including: a first PVOHcopolymer including an anionic monomer unit, the first PVOH copolymerhaving a first 4% solution viscosity at 20° C. (μ₁); and a second PVOHpolymer consisting essentially of vinyl alcohol monomer units andoptionally vinyl acetate monomer units, the second PVOH polymer having asecond 4% solution viscosity at 20° C. (μ₂) of about 20 cP or less;wherein: the anionic monomer unit is present in the film in an amount ina range of about 1.2 mol. % to about 4.2 mol. % of total PVOH polymersand PVOH copolymers in the film.

Another aspect of the disclosure relates to an article including awater-soluble film and a household care composition proximal to thefilm, where the film includes: a polyvinyl alcohol (PVOH) resin blendincluding: a first PVOH copolymer comprising a first anionic monomerunit; and a second PVOH polymer consisting essentially of vinyl alcoholmonomer units and optionally vinyl acetate monomer units; wherein thefirst PVOH copolymer is present in an amount in a range of about 30 wt.% to about 70 wt. % of total PVOH polymers and PVOH copolymers in thefilm.

Another aspect of the disclosure relates to an article including: awater-soluble film according to any of the variously disclosedembodiments in the form of a pouch defining an interior pouch volume(e.g., further including a composition, such as a household carecomposition, contained in the interior pouch volume).

In a particular refinement of the various embodiments, the anionicmonomer is selected from the group consisting of acrylamidomethylpropanesulfonic acids, alkali metal salts thereof, andcombinations thereof. In another refinement of the various embodiments,the anionic monomer is selected from the group consisting of monomethylmaleate, alkali metal salts thereof, and combinations thereof. Inanother refinement of the various embodiments, the anionic monomer unitis present in first PVOH copolymer in an amount in a range of about 2mol. % to about 10 mol. %. In another refinement of the variousembodiments, a viscosity difference (μ₂−μ₁) for the first PVOH copolymerand the second PVOH polymer is in a range from about 0 cP to about 10 cP(e.g., about 0 cP to about 5 cP). In another refinement of the variousembodiments, the first viscosity μ₁ is in a range of about 4 cP to about24 cP (e.g., about 8 cP to about 16 cP). In another refinement of thevarious embodiments, the second viscosity μ₂ is in a range of about 4 cPto about 24 cP (e.g., about 8 cP to about 16 cP). In another refinementof the various embodiments, the water-soluble film has a residue valueof about 45 wt. % or less as measured by the Dissolution Chamber Test(e.g., about 10 wt. % or 20 wt. % to about 40 wt. % or 45 wt. %). Inanother refinement of the various embodiments, the second PVOH polymeris present in an amount in a range of about 10 wt. % to about 70 wt. %of total PVOH polymers and PVOH copolymers in the film (e.g., where thefirst PVOH copolymer is present in an amount in a range of about 30 wt.% to about 90 wt. % of total PVOH polymers and PVOH copolymers in thefilm).

Another aspect of the disclosure relates to a method of forming thearticles described herein, where the method includes the steps of:providing the water-soluble film, where the film defines an interiorpouch container volume; filling the container volume with a composition(e.g., a household care composition); and sealing the film to form asealed compartment, wherein the sealed compartment contains thecomposition.

Another aspect of the disclosure relates to a method of treating asubstrate, where the method includes the step of contacting thesubstrate with an article as described herein.

For the compositions and methods described herein, optional features,including but not limited to components, compositional ranges thereof,substituents, conditions, and steps, are contemplated to be selectedfrom the various aspects, embodiments, and examples provided herein.

Further aspects and advantages will be apparent to those of ordinaryskill in the art from a review of the following detailed description andaccompanying drawings. While the compositions and methods aresusceptible of embodiments in various forms, the description hereafterincludes specific embodiments with the understanding that the disclosureis illustrative, and is not intended to limit the invention to thespecific embodiments described herein.

DESCRIPTION OF THE DRAWINGS

The following detailed description of the various disclosed methods,processes, compositions, and articles refers to the accompanyingdrawings in which:

FIG. 1 is a side cross-sectional view of water-soluble pouch article forthe aqueous delivery of a delayed release capsule in combination withanother composition according to the disclosure;

FIG. 2 is graph illustrating Dissolution Chamber Residue (wt. %) vs.Anionic Comonomer Content (mol. %) for water-soluble films including asingle PVOH (co)polymer resin;

FIG. 3 is graph illustrating Dissolution Chamber Residue (wt. %) vs.Anionic Comonomer Content (mol. %) for water-soluble films including aPVOH resin blend including a PVOH copolymer and a PVOH homopolymer; and

FIG. 4 is graph illustrating Dissolution Chamber Residue (wt. %) vs.Anionic Comonomer Content (mol. %) for water-soluble films including aPVOH resin blend including a PVOH copolymer and a PVOH homopolymer.

DETAILED DESCRIPTION

Disclosed herein are water-soluble films including blends of polyvinylalcohol polymers and articles such as delivery pouches formed from orotherwise including the films, where the articles or pouches can furtherinclude a household care composition.

Some water-soluble polymeric films that are used to make articles suchas packets (e.g., which can contain a household care compositiontherein) will incompletely dissolve in water during normal use, forexample during a laundry wash cycle for packets containing alaundry-related composition (e.g., thereby leaving film residue on itemswithin the wash).

Water-soluble polymeric films based on PVOH can be subject to changes insolubility characteristics. The acetate group in the co-poly(vinylacetate vinyl alcohol) polymer is known by those skilled in the art tobe hydrolysable by either acid or alkaline hydrolysis. As the degree ofhydrolysis increases, a polymer composition made from the PVOHhomopolymer resin will have increased mechanical strength but reducedsolubility at lower temperatures (e.g., requiring hot water temperaturesfor complete dissolution). Accordingly, exposure of a PVOH homopolymerresin to an alkaline environment (e.g., resulting from a laundrybleaching additive) can transform the resin from one which dissolvesrapidly and entirely in a given aqueous environment (e.g., a cold watermedium) to one which dissolves slowly and/or incompletely in the aqueousenvironment, potentially resulting in undissolved polymeric residue atthe end of a wash cycle. This is an inherent weakness in the applicationof films based on just the vinyl acetate/alcohol co-polymer typified bycommercial PVOH homopolymer resins.

PVOH copolymer resins with pendant carboxyl groups, such as vinylalcohol/hydrolyzed methyl acrylate sodium salt resins, can form lactonerings between neighboring pendant carboxyl and alcohol groups, thusreducing the water solubility of the PVOH copolymer resin. In thepresence of a strong base such as a laundry bleaching additive, thelactone rings can open over the course of several weeks at relativelywarm (ambient) and high humidity conditions (e.g., via lactonering-opening reactions to form the corresponding pendant carboxyl andalcohol groups with increased water solubility). Thus, contrary to theeffect observed with PVOH homopolymer films, it is believed that such aPVOH copolymer film can become more soluble due to chemical interactionsbetween the film and an alkaline composition inside the pouch duringstorage. Consequently, as they age, the packets may become increasinglyprone to premature dissolution during a hot wash cycle (nominally 40°C.), and may in turn decrease the efficacy of certain laundry activesdue to the presence of the bleaching agent and the resulting pHinfluence.

The present disclosure includes a water-soluble film including apolyvinyl alcohol (PVOH) resin blend and optionally one or moreadditional components such as plasticizers, fillers, surfactants, andother additives as described in more detail below. The presentdisclosure further includes an article or packet including thewater-soluble film, for example containing a household care composition.The PVOH resin blend includes a first PVOH resin which is a PVOHcopolymer (“first PVOH copolymer”) including one or more types ofanionic monomer units (e.g., a PVOH ter- (or higher co-) polymer) and asecond PVOH resin which is a PVOH polymer (“second PVOH polymer”)including vinyl alcohol monomer units and (optionally) vinyl acetatemonomer units (e.g., a PVOH homopolymer which is either completelyhydrolyzed polyvinyl alcohol or a partially hydrolyzed combination ofpoly(vinyl alcohol-co-vinyl acetate). In some aspects, the PVOH resinblend includes only the first PVOH copolymer and the second PVOH polymer(e.g., a binary blend of the two polymers). Alternatively oradditionally, the PVOH resin blend, the water-soluble film, or both canbe characterized as being free or substantially free from other polymers(e.g., other water-soluble polymers generally, other PVOH-based polymersspecifically, or both). In other aspects, the water-soluble film caninclude one or more additional water-soluble polymers. For example, thePVOH resin blend can include a (third) PVOH polymer, a fourth PVOHpolymer, a fifth PVOH polymer, etc. (e.g., one or more additional PVOHhomopolymers or PVOH copolymers, with or without anionic monomer units).For example, the water-soluble film can include at least a third (orfourth, fifth, etc.) water-soluble polymer which is other than a PVOHpolymer (e.g., other than PVOH homopolymers or PVOH copolymers, with orwithout anionic monomer units).

The PVOH copolymer can be a PVOH terpolymer including vinyl alcoholmonomer units, vinyl acetate monomer units (i.e., when not completelyhydrolyzed), and a single type of anionic monomer unit (e.g., a where asingle type of monomer unit can include equivalent acid forms, saltforms, and optionally ester forms of the anionic monomer unit). In someaspects, the PVOH copolymer can include two or more types of anionicmonomer units. General classes of anionic monomer units which can beused for the PVOH copolymer include the vinyl polymerization unitscorresponding to monocarboxylic acid vinyl monomers, their esters andanhydrides, dicarboxylic monomers having a polymerizable double bond,their esters and anhydrides, vinyl sulfonic acid monomers, and alkalimetal salts of any of the foregoing. Examples of suitable anionicmonomer units include the vinyl polymerization units corresponding tovinyl anionic monomers including vinyl acetic acid, maleic acid,monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethylmaleate, maleic anyhydride, fumaric acid, monoalkyl fumarate, dialkylfumarate, monomethyl fumarate, dimethyl fumarate, fumaric anyhydride,itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconicanhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonicacid, 2-acrylamido-1-methylpropanesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts of the foregoing (e.g., sodium, potassium, or otheralkali metal salts), esters of the foregoing (e.g., methyl, ethyl, orother C₁-C₄ or C₆ alkyl esters), and combinations thereof (e.g.,multiple types of anionic monomers or equivalent forms of the sameanionic monomer). In an aspect, the anionic monomer can be one or moreacrylamido methylpropanesulfonic acids (e.g.,2-acrylamido-1-methylpropanesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid), alkali metal saltsthereof (e.g., sodium salts), and combinations thereof. In an aspect,the anionic monomer can be one or more of monomethyl maleate, alkalimetal salts thereof (e.g., sodium salts), and combinations thereof.

The level of incorporation of the one or more anionic monomer units inthe PVOH copolymers (e.g., the first PVOH copolymer) is not particularlylimited. In some aspects, the one or more anionic monomer units arepresent in a first PVOH copolymer in an amount in a range of about 2mol. % to about 10 mol. % or about 3 mol. % to about 5 mol. % (e.g., atleast 2.0, 2.5, 3.0, 3.5, or 4.0 mol. % and/or up to about 3.0, 4.0,4.5, 5.0, 6.0, 8.0, or 10 mol. % in various embodiments), individuallyor collectively. For example, the one or more anionic monomer units canbe present in a first PVOH copolymer in an amount in a range of about 5mol. % to about 10 mol. % (e.g., at least 5.0 or 6.0 mol. % and/or up toabout 7.0, 8.0, or 10 mol. % in various embodiments), individually orcollectively. Alternatively or additionally, the one or more anionicmonomer units can be present in the water-soluble film in an amount in arange of about 3 mol. % to about 4.2 mol. %, collectively, of total PVOHpolymers and copolymers in the film (e.g., at least 3.0 or 3.5 mol. %and/or up to about 3.7, 4.0, or 4.2 mol. % in various embodiments). Inanother aspect, the one or more anionic monomer units in the first PVOHpolymer can be present in the water-soluble film in an amount in a rangeof about 1 mol. % to about 3 mol. %, collectively, of total PVOHpolymers and copolymers in the film. For example, an anionic PVOHcopolymer can be blended with a PVOH polymer (e.g., about 40%/60% to60%/40% (w/w) blend) to achieve an average blend anionic monomer unitcontent in a range of about 3 mol. % to about 4.2 mol. % in theneighborhood where the Dissolution Chamber residue curve approaches zeroas a function of anionic monomer content. In an embodiment, the firstanionic monomer can be present in an amount less than about 3 mol. % oftotal PVOH polymers and PVOH copolymers in the film

The water-soluble film can contain at least about 50 wt. %, 55 wt. %, 60wt. %, 65 wt. %, 70 wt. %, 75 wt. %, 80 wt. %, 85 wt. %, or 90 wt. %and/or up to about 60 wt. %, 70 wt. %, 80 wt. %, 90 wt. %, 95 wt. %, or99 wt. % of the PVOH resin blend. In one aspect, the first PVOHcopolymer is present in the water-soluble film in an amount in a rangeof about 30 wt. % to about 90 wt. % (or about 40 wt. % to about 60 wt.%, about 40 wt. % to about 70 wt. %, about 30 wt. % to about 70 wt. %)of total PVOH polymers and PVOH copolymers in the film (i.e., relativeto the PVOH resin blend weight). For example, the first PVOH copolymercan be present in an amount of at least 30 wt. %, 40 wt. %, 45 wt. %, 50wt. %, 55 wt. %, 60 wt. %, or 65 wt. % and/or up to about 55 wt. %, 60wt. %, 65 wt. %, 70 wt. %, 75 wt. %, 80 wt. %, 85 wt. % or 90 wt. % oftotal PVOH polymers and PVOH copolymers in the film. In another aspect,the foregoing concentrations of first PVOH copolymer alternatively oradditionally can be relative to total water-soluble polymer content infilm, PVOH or otherwise. In an aspect, the second PVOH polymer ispresent in an amount in a range of about 10 wt. % to about 70 wt. % (orabout 30 wt. % to about 60 wt. %, about 40 wt. % to about 60 wt. %,about 30 wt. % to about 70 wt. %) of total PVOH polymers and PVOHcopolymers in the film (i.e., relative to the PVOH resin blend weight).For example, the second PVOH polymer can be present in an amount of atleast 10 wt. %, 20 wt. %, 30 wt. %, or 40 wt. % and/or up to about 40wt. %, 50 wt. %, 60 wt. %, or 70 wt. % of total PVOH polymers and PVOHcopolymers in the film. In another aspect, the foregoing concentrationsof second PVOH polymer alternatively or additionally can be relative tototal water-soluble polymer content in film, PVOH or otherwise.

Alternatively or additionally to the relative amounts of polymericresins, PVOH or otherwise, the water-soluble film can be characterizedin terms of the molar content of the anionic monomer units in the film(in particular relative to the polymeric resin content thereof). In oneaspect, the one or more anionic monomer units are present in the film inan amount ranging from about 1.0 mol. % to about 4.2 mol. % (or about 1mol. % to about 3.4 mol. %, or about 1.4 mol. % to about 2.6 mol. %),individually or collectively, of total PVOH polymers and PVOH copolymersin the film. For example, the one or more anionic monomer units can bepresent in the film in an amount of at least 1.0, 1.2, 1.4, 1.6, 1.8,2.0, 2.2, 2.5, or 3.0 mol. % and/or up to about 2.5, 3.0, 3.4, 3.6, 3.8,4.0 or 4.2 mol. %. individually or collectively. The anionic monomerunit content alternatively or additionally can be expressed relative tototal water-soluble polymer content in film, PVOH or otherwise.

As described in more detail below, PVOH polymer and PVOH copolymerresins can be characterized in terms of their 4% solution viscosityvalues at 20° C. in water (i.e., as values which generally correlate tothe molecular weights of the resins). For reference, the first PVOHcopolymer is denoted as having a first 4% solution viscosity at 20° C.(μ₁), and the second PVOH polymer is denoted as having a second 4%solution viscosity at 20° C. (μ₂). In one aspect of the disclosure, anabsolute viscosity difference |μ₂−μ₁| for the first PVOH copolymer andthe second PVOH polymer in the PVOH resin blend is in a range of 0 cP toabout 10 cP (e.g., up to about 1, 2, 5, or 10 cP; about 0 cP). Inanother aspect of the disclosure, the second PVOH polymer can have asecond 4% solution viscosity at 20° C. (μ₂) of about 20 cP or less(e.g., at least about 4, 8, 10, or 12 cP and/or up to about 12, 16, or20 cP). In either or both of the foregoing aspects, a viscositydifference (μ₂−μ₁) for the first PVOH copolymer and the second PVOHpolymer can be in a range from about 0 cP to about 10 cP (e.g., at leastabout 0, 0.5, 1, or 2 cP and/or up to about 1, 2, 5, or 10 cP, such asabout 0 cP to about 5 cP or about 0 cP to about 2 cP). In an aspect, thefirst PVOH copolymer and the second PVOH polymer have 4% solutionviscosity values at 20° C. that are within about 10 cP of each other. Inanother aspect, the first PVOH copolymer and the second PVOH polymerhave 4% solution viscosity values at 20° C. that are more than about 10cP apart from each other. In various embodiments, the first viscosity μ₁can be in a range of about 4 cP to about 24 cP (e.g., at least about 4,8, 10 or 12 cP and/or up to about 12, 16, 20, or 24 cP, such as about 10cP to about 16 cP or about 10 cP to about 20 cP). Alternatively oradditionally, the second viscosity μ₂ can be in a range of about 4 cP toabout 24 cP, about 8 cP to about 16 cP, or about 20 cP to about 30 cP(e.g., at least about 4, 8, 10 or 12 cP and/or up to about 12, 16, 20,or 24 cP, such as about 10 cP to about 16 cP or about 10 cP to about 20cP). When the PVOH resin blend includes three or more PVOH resinsselected from PVOH polymer and PVOH copolymer resins, the foregoingviscosity values can apply to each PVOH polymer or PVOH copolymerindividually and the foregoing viscosity differences can apply to eachPVOH polymer/PVOH copolymer pair in the PVOH resin blend and resultingwater-soluble film.

The disclosed water-soluble films, articles such as delivery pouchesincluding the films, and related methods are contemplated to includeembodiments including any combination of one or more of the additionaloptional elements, features, and steps further described below(including those shown in the figures and examples), unless statedotherwise.

In any embodiment, the water-soluble article or pouch can contain acomposition, for example a household care composition. The compositioncan be selected from a liquid, solid or combination thereof. As usedherein, “liquid” includes free-flowing liquids, as well as pastes, gels,foams and mousses. Non-limiting examples of liquids include light dutyand heavy duty liquid detergent compositions, fabric enhancers,detergent gels commonly used for laundry, bleach and laundry additives.Gases, e.g., suspended bubbles, or solids, e.g. particles, may beincluded within the liquids. A “solid” as used herein includes, but isnot limited to, powders, agglomerates, and mixtures thereof.Non-limiting examples of solids include: granules, micro-capsules,beads, noodles, and pearlised balls. Solid compositions may provide atechnical benefit including, but not limited to, through-the-washbenefits, pre-treatment benefits, and/or aesthetic effects.

In any of the laundry-centric embodiments, the composition may beselected from the group of liquid light duty and liquid heavy dutyliquid detergent compositions, powdered detergent compositions, fabricenhancers, detergent gels commonly used for laundry, and bleach (e.g.,organic or inorganic bleach) and laundry additives, for example.

As used herein, the term “homopolymer” generally includes polymershaving a single type of monomeric repeating unit (e.g., a polymericchain consisting of or consisting essentially of a single monomericrepeating unit). For the particular case of PVOH, the term “homopolymer”(or “PVOH homopolymer” or “PVOH polymer”) further includes copolymershaving a distribution of vinyl alcohol monomer units and vinyl acetatemonomer units, depending on the degree of hydrolysis (e.g., a polymericchain consisting of or consisting essentially of vinyl alcohol and vinylacetate monomer units). In the limiting case of 100% hydrolysis, a PVOHhomopolymer can include a true homopolymer having only vinyl alcoholunits.

As used herein, the term “copolymer” generally includes polymers havingtwo or more types of monomeric repeating units (e.g., a polymeric chainconsisting of or consisting essentially of two or more differentmonomeric repeating units, whether as random copolymers, blockcopolymers, etc.). For the particular case of PVOH, the term “copolymer”(or “PVOH copolymer”) further includes copolymers having a distributionof vinyl alcohol monomer units and vinyl acetate monomer units,depending on the degree of hydrolysis, as well as at least one othertype of monomeric repeating unit (e.g., a ter- (or higher) polymericchain consisting of or consisting essentially of vinyl alcohol monomerunits, vinyl acetate monomer units, and one or more other monomer units,for example anionic monomer units). In the limiting case of 100%hydrolysis, a PVOH copolymer can include a copolymer having vinylalcohol units and one or more other monomer units, but no vinyl acetateunits.

As used herein, the term “comprising” indicates the potential inclusionof other agents, elements, steps, or features, in addition to thosespecified.

As used herein and unless specified otherwise, the terms “wt. %” and “wt%” are intended to refer to the composition of the identified element in“dry” (non water) parts by weight of the entire film (when applicable)or parts by weight of the entire composition enclosed within a pouch(when applicable). As used herein and unless specified otherwise, theterm “phr” is intended to refer to the composition of the identifiedelement in parts per one hundred parts water-soluble polymer (or resin;whether PVOH or otherwise) in the water-soluble film.

All ranges set forth herein include all possible subsets of ranges andany combinations of such subset ranges. By default, ranges are inclusiveof the stated endpoints, unless stated otherwise. Where a range ofvalues is provided, it is understood that each intervening value betweenthe upper and lower limit of that range and any other stated orintervening value in that stated range, is encompassed within thedisclosure. The upper and lower limits of these smaller ranges mayindependently be included in the smaller ranges, and are alsoencompassed within the disclosure, subject to any specifically excludedlimit in the stated range. Where the stated range includes one or bothof the limits, ranges excluding either or both of those included limitsare also contemplated to be part of the disclosure.

Water-Soluble Film Compositions

Water-soluble film compositions, optional ingredients for use therein,and methods of making the same are well known in the art, whether beingused for making relatively thin water-soluble films (e.g., as pouchmaterials) or otherwise.

In one class of embodiments, the water-soluble film includes polyvinylalcohol (PVOH), including homopolymers thereof (e.g., includingsubstantially only vinyl alcohol and vinyl acetate monomer units) andcopolymers thereof (e.g., including one or more other monomer units inaddition to vinyl alcohol and vinyl acetate units). PVOH is a syntheticresin generally prepared by the alcoholysis, usually termed hydrolysisor saponification, of polyvinyl acetate. Fully hydrolyzed PVOH, whereinvirtually all the acetate groups have been converted to alcohol groups,is a strongly hydrogen-bonded, highly crystalline polymer whichdissolves only in hot water—greater than about 140° F. (60° C.). If asufficient number of acetate groups are allowed to remain after thehydrolysis of polyvinyl acetate, the PVOH polymer then being known aspartially hydrolyzed, it is more weakly hydrogen-bonded and lesscrystalline and is soluble in cold water—less than about 50° F. (10°C.). An intermediate cold or hot water soluble film can include, forexample, intermediate partially-hydrolyzed PVOH (e.g., with degrees ofhydrolysis of about 94% to about 98%), and is readily soluble only inwarm water—e.g., rapid dissolution at temperatures of about 40° C. andgreater. Both fully and partially hydrolyzed PVOH types are commonlyreferred to as PVOH homopolymers although the partially hydrolyzed typeis technically a vinyl alcohol-vinyl acetate copolymer.

The degree of hydrolysis (DH) of the PVOH polymers and PVOH copolymersincluded in the water-soluble films of the present disclosure can be ina range of about 75% to about 99% (e.g., about 79% to about 92%, about86.5% to about 89%, or about 88%, such as for cold-water solublecompositions; about 90% to about 99%, about 92% to about 99%, or about95% to about 99%). As the degree of hydrolysis is reduced, a film madefrom the resin will have reduced mechanical strength but fastersolubility at temperatures below about 20° C. As the degree ofhydrolysis increases, a film made from the polymer will tend to bemechanically stronger and the thermoformability will tend to decrease.The degree of hydrolysis of the PVOH can be chosen such that thewater-solubility of the polymer is temperature dependent, and thus thesolubility of a film made from the polymer, any compatibilizer polymer,and additional ingredients is also influenced. In one option the film iscold water-soluble. A cold water-soluble film, soluble in water at atemperature of less than 10° C., can include PVOH with a degree ofhydrolysis in a range of about 75% to about 90%, or in a range of about80% to about 90%, or in a range of about 85% to about 90%. In anotheroption the film is hot water-soluble. A hot water-soluble film, solublein water at a temperature of at least about 60° C., can include PVOHwith a degree of hydrolysis of at least about 98%.

Other water soluble polymers for use in addition to the PVOH polymersand PVOH copolymers in the blend can include, but are not limited tomodified polyvinyl alcohols, polyacrylates, water-soluble acrylatecopolymers, polyvinyl pyrrolidone, polyethyleneimine, pullulan,water-soluble natural polymers including, but not limited to, guar gum,gum Acacia, xanthan gum, carrageenan, and starch, water-soluble polymerderivatives including, but not limited to, modified starches,ethoxylated starch, and hydroxypropylated starch, copolymers of theforgoing and combinations of any of the foregoing. Yet otherwater-soluble polymers can include polyalkylene oxides, polyacrylamides,polyacrylic acids and salts thereof, celluloses, cellulose ethers,cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylicacids and salts thereof, polyaminoacids, polyamides, gelatines,methylcelluloses, carboxymethylcelluloses and salts thereof, dextrins,ethylcelluloses, hydroxyethyl celluloses, hydroxypropylmethylcelluloses, maltodextrins, and polymethacrylates. Suchwater-soluble polymers, whether PVOH or otherwise are commerciallyavailable from a variety of sources. Any of the foregoing water-solublepolymers are generally suitable for use as film-forming polymers. Ingeneral, the water-soluble film can include copolymers and/or blends ofthe foregoing resins.

The water-soluble polymers (e.g., the PVOH resin blend alone or incombination with other water-soluble polymers) can be included in thefilm in an amount in a range of about 30 wt. % or 50 wt. % to about 90wt. % or 95 wt. %, for example. The weight ratio of the amount of allwater-soluble polymers as compared to the combined amount of allplasticizers, compatibilizing agents, and secondary additives can be ina range of about 0.5 to about 18, about 0.5 to about 15, about 0.5 toabout 9, about 0.5 to about 5, about 1 to 3, or about 1 to 2, forexample. The specific amounts of plasticizers and other non-polymercomponent can be selected in a particular embodiment based on anintended application of the water-soluble film to adjust filmflexibility and to impart processing benefits in view of desiredmechanical film properties.

Water-soluble polymers for use in the film described herein (including,but not limited to PVOH polymers and PVOH copolymers) can becharacterized by a viscosity in a range of about 3.0 to about 27.0 cP,about 4.0 to about 24.0 cP, about 4.0 to about 23.0 cP, about 4.0 cP toabout 15 cP, or about 6.0 to about 10.0 cP, for example. The viscosityof a polymer is determined by measuring a freshly made solution using aBrookfield LV type viscometer with UL adapter as described in BritishStandard EN ISO 15023-2:2006 Annex E Brookfield Test method. It isinternational practice to state the viscosity of 4% aqueous polyvinylalcohol solutions at 20° C. Polymeric viscosities specified herein in cPshould be understood to refer to the viscosity of a 4% aqueouswater-soluble polymer solution at 20° C., unless specified otherwise.

It is well known in the art that the viscosity of a water-solublepolymer (PVOH or otherwise) is correlated with the weight-averagemolecular weight (Mw) of the same polymer, and often the viscosity isused as a proxy for Mw. Thus, the weight-average molecular weight of thewater-soluble polymers, including the first PVOH copolymer and secondPVOH polymer, can be in a range of about 30,000 to about 175,000, orabout 30,000 to about 100,000, or about 55,000 to about 80,000, forexample.

The water-soluble film can contain other auxiliary agents and processingagents, such as, but not limited to, plasticizers, plasticizercompatibilizers, surfactants, lubricants, release agents, fillers,extenders, cross-linking agents, antiblocking agents, antioxidants,detackifying agents, antifoams, nanoparticles such as layeredsilicate-type nanoclays (e.g., sodium montmorillonite), bleaching agents(e.g., sodium metabisulfite, sodium bisulfite or others), aversiveagents such as bitterants (e.g., denatonium salts such as denatoniumbenzoate, denatonium saccharide, and denatonium chloride; sucroseoctaacetate; quinine; flavonoids such as quercetin and naringen; andquassinoids such as quassin and brucine) and pungents (e.g., capsaicin,piperine, allyl isothiocyanate, and resinferatoxin), and otherfunctional ingredients, in amounts suitable for their intended purposes.Embodiments including plasticizers are preferred. The amount of suchagents can be up to about 50 wt. %, 20 wt %, 15 wt %, 10 wt %, 5 wt. %,4 wt % and/or at least 0.01 wt. %, 0.1 wt %, 1 wt %, or 5 wt %,individually or collectively.

The plasticizer can include, but is not limited to, glycerin,diglycerin, sorbitol, ethylene glycol, diethylene glycol, triethyleneglycol, dipropylene glycol, tetraethylene glycol, propylene glycol,polyethylene glycols up to 400 MW, neopentyl glycol, trimethylolpropane,polyether polyols, sorbitol, 2-methyl-1,3-propanediol, ethanolamines,and a mixture thereof. A preferred plasticizer is glycerin, sorbitol,triethyleneglycol, propylene glycol, dipropylene glycol,2-methyl-1,3-propanediol, trimethylolpropane, or a combination thereof.The total amount of the plasticizer can be in a range of about 10 wt. %to about 40 wt. %, or about 15 wt. % to about 35 wt. %, or about 20 wt.% to about 30 wt. %, for example about 25 wt. %, based on total filmweight. Combinations of glycerin, dipropylene glycol, and sorbitol canbe used. Optionally, glycerin can be used in an amount of about 5 wt %to about 30 wt %, or 5 wt % to about 20 wt %, e.g., about 13 wt %.Optionally, dipropylene glycol can be used in an amount of about 1 wt. %to about 20 wt. %, or about 3 wt. % to about 10 wt. %, for example 6 wt.%. Optionally, sorbitol can be used in an amount of about 1 wt % toabout 20 wt %, or about 2 wt % to about 10 wt %, e.g., about 5 wt %. Thespecific amounts of plasticizers can be selected in a particularembodiment based on desired film flexibility and processability featuresof the water-soluble film. At low plasticizer levels, films may becomebrittle, difficult to process, or prone to breaking. At elevatedplasticizer levels, films may be too soft, weak, or difficult to processfor a desired use.

Suitable surfactants can include the nonionic, cationic, anionic andzwitterionic classes. Suitable surfactants include, but are not limitedto, polyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates,alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides(nonionics), polyoxyethylenated amines, quaternary ammonium salts andquaternized polyoxyethylenated amines (cationics), and amine oxides,N-alkylbetaines and sulfobetaines (zwitterionics). Other suitablesurfactants include dioctyl sodium sulfosuccinate, lactylated fatty acidesters of glycerol and propylene glycol, lactylic esters of fatty acids,sodium alkyl sulfates, polysorbate 20, polysorbate 60, polysorbate 65,polysorbate 80, lecithin, acetylated fatty acid esters of glycerol andpropylene glycol, and acetylated esters of fatty acids, and combinationsthereof. In various embodiments, the amount of surfactant in thewater-soluble film is in a range of about 0.1 wt % to 2.5 wt %,optionally about 1.0 wt % to 2.0 wt %.

Suitable lubricants/release agents can include, but are not limited to,fatty acids and their salts, fatty alcohols, fatty esters, fatty amines,fatty amine acetates and fatty amides. Preferred lubricants/releaseagents are fatty acids, fatty acid salts, and fatty amine acetates. Inone type of embodiment, the amount of lubricant/release agent in thewater-soluble film is in a range of about 0.02 wt % to about 1.5 wt %,optionally about 0.1 wt % to about 1 wt %.

Suitable fillers/extenders/antiblocking agents/detackifying agentsinclude, but are not limited to, starches, modified starches,crosslinked polyvinylpyrrolidone, crosslinked cellulose,microcrystalline cellulose, silica, metallic oxides, calcium carbonate,talc and mica. Preferred materials are starches, modified starches andsilica. In one type of embodiment, the amount offiller/extender/antiblocking agent/detackifying agent in thewater-soluble film is in a range of about 0.1 wt % to about 25 wt %, orabout 1 wt % to about 10 wt %, or about 2 wt. % to about 8 wt. %, orabout 3 wt. % to about 5 wt. %. In the absence of starch, one preferredrange for a suitable filler/extender/antiblocking agent/detackifyingagent is about 0.1 wt % or 1 wt % to about 4 wt % or 6 wt %, or about 1wt. % to about 4 wt. %, or about 1 wt. % to about 2.5 wt. %.

The water-soluble film can further have a residual moisture content ofat least 4 wt. %, for example in a range of about 4 to about 10 wt. %,as measured by Karl Fischer titration.

Other features of water-soluble polymer compositions such as films, maybe found in U.S. Publication No. 2011/0189413 and U.S. application Ser.No. 13/740,053, both of which are incorporated by reference herein intheir entireties.

Method of Making Film

One contemplated class of embodiments is characterized by thewater-soluble film being formed by, for example, admixing, co-casting,or welding the first PVOH copolymer and the second PVOH polymeraccording to the types and amounts described herein, together with thepreferred and optional secondary additives described herein. If thepolymers are first admixed then the water-soluble film is preferablyformed by casting the resulting admixture (e.g., along with otherplasticizers and other additives) to form a film. If the polymers arewelded, the water-soluble film can be formed by, for example, solvent orthermal welding. Another contemplated class of embodiments ischaracterized by the water-soluble film being formed by extrusion, forexample, blown extrusion. In one contemplated non-limiting embodiment aPVOH polymer and an acrylamido methylpropanesulfonic acid PVOHterpolymer blended film is formed by blown extrusion.

The film can have any suitable thickness. For example, the film can havea thickness in a range of about 5 to about 200 μm, or in a range ofabout 20 to about 100 μm, or about 40 to about 85 μm, for example 76 μm.

Optionally, the water-soluble film can be a free-standing filmconsisting of one layer or a plurality of like layers.

The film is useful for creating an article such as a packet to contain adetergent composition comprising cleaning actives thereby forming apouch. The cleaning actives may take any form such as powders, gels,pastes, liquids, tablets or any combination thereof. The film is alsouseful for any other application in which improved wet handling and lowcold water residues are desired. The film forms at least one side wallof the pouch and/or packet, optionally the entire pouch and/or packet,and preferably an outer surface of the at least one sidewall.

The film described herein can also be used to make an article such as apacket with two or more compartments made of the same film or incombination with films of other polymeric materials. Additional filmscan, for example, be obtained by casting, blow-molding, extrusion orblown extrusion of the same or a different polymeric material, as knownin the art. In one type of embodiment, the polymers, copolymers orderivatives thereof suitable for use as the additional film are selectedfrom polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides,polyacrylic acid, cellulose, cellulose ethers, cellulose esters,cellulose amides, polyvinyl acetates, polycarboxylic acids and salts,polyaminoacids or peptides, polyamides, polyacrylamide, copolymers ofmaleic/acrylic acids, polysaccharides including starch and gelatin,natural gums such as xanthan, and carrageenans. For example, polymerscan be selected from polyacrylates and water-soluble acrylatecopolymers, methylcellulose, carboxymethylcellulose sodium, dextrin,ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose,maltodextrin, polymethacrylates, and combinations thereof, or selectedfrom polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropylmethyl cellulose (HPMC), and combinations thereof. One contemplatedclass of embodiments is characterized by the level of polymer in thepacket material, for example the PVOH resin blend, as described above,being at least 60%.

Articles and Pouches

The articles of the present disclosure include a water soluble film andcan include a composition, typically a household care composition, thatis proximal to the film.

The articles of the present disclosure can include pouches that includeat least one sealed compartment. Thus, the pouches may comprise a singlecompartment or multiple compartments. FIG. 1 illustrates an article inwhich a water-soluble pouch 100 is formed from water-soluble polymerfilms 10, 20 sealed at an interface 30. One or both of the films 10, 20include the PVOH resin blend of the first PVOH copolymer and the secondPVOH polymer. The films 10, 20 define an interior pouch container volume40 which contains any desired composition 50 for release into an aqueousenvironment. The composition 50 is not particularly limited, for exampleincluding any of the variety of cleaning compositions described below.In embodiments comprising multiple compartments (not shown), eachcompartment may contain identical and/or different compositions. Inturn, the compositions may take any suitable form including, but notlimited to liquid, solid and combinations thereof (e.g. a solidsuspended in a liquid). In some embodiments, the pouches comprises afirst, second and third compartment, each of which respectively containsa different first, second, and third composition.

The compartments of multi-compartment pouches may be of the same ordifferent size(s) and/or volume(s). The compartments of the presentmulti-compartment pouches can be separate or conjoined in any suitablemanner. In some embodiments, the second and/or third and/or subsequentcompartments are superimposed on the first compartment. In oneembodiment, the third compartment may be superimposed on the secondcompartment, which is in turn superimposed on the first compartment in asandwich configuration. Alternatively the second and third compartmentsmay be superimposed on the first compartment. However it is also equallyenvisaged that the first, second and optionally third and subsequentcompartments may be attached to one another in a side by siderelationship. The compartments may be packed in a string, eachcompartment being individually separable by a perforation line. Henceeach compartment may be individually torn-off from the remainder of thestring by the end-user, for example, so as to pre-treat or post-treat afabric with a composition from a compartment. In some embodiments, thefirst compartment may be surrounded by at least the second compartment,for example in a tire-and-rim configuration, or in a pouch-in-a-pouchconfiguration.

In some embodiments, multi-compartment pouches comprise threecompartments consisting of a large first compartment and two smallercompartments. The second and third smaller compartments are superimposedon the first larger compartment. The size and geometry of thecompartments are chosen such that this arrangement is achievable. Thegeometry of the compartments may be the same or different. In someembodiments the second and optionally third compartment each has adifferent geometry and shape as compared to the first compartment. Inthese embodiments, the second and optionally third compartments arearranged in a design on the first compartment. The design may bedecorative, educative, or illustrative, for example to illustrate aconcept or instruction, and/or used to indicate origin of the product.In some embodiments, the first compartment is the largest compartmenthaving two large faces sealed around the perimeter, and the secondcompartment is smaller covering less than about 75%, or less than about50% of the surface area of one face of the first compartment. Inembodiments in which there is a third compartment, the aforementionedstructure may be the same but the second and third compartments coverless than about 60%, or less than about 50%, or less than about 45% ofthe surface area of one face of the first compartment.

The articles, pouches, and/or packets of the present disclosure maycomprise one or more different films. For example, in single compartmentembodiments, the packet may be made from one wall that is folded ontoitself and sealed at the edges, or alternatively, two walls that aresealed together at the edges. In multiple compartment embodiments, thepacket may be made from one or more films such that any given packetcompartment may comprise walls made from a single film or multiple filmshaving differing compositions. In one embodiment, a multi-compartmentpouch comprises at least three walls: an outer upper wall; an outerlower wall; and a partitioning wall. The outer upper wall and the outerlower wall are generally opposing and form the exterior of the pouch.The partitioning wall is interior to the pouch and is secured to thegenerally opposing outer walls along a seal line. The partitioning wallseparates the interior of the multi-compartment pouch into at least afirst compartment and a second compartment.

Articles such as pouches and packets may be made using any suitableequipment and method. For example, single compartment pouches may bemade using vertical form filling, horizontal form filling, or rotarydrum filling techniques commonly known in the art. Such processes may beeither continuous or intermittent. The film may be dampened, and/orheated to increase the malleability thereof. The method may also involvethe use of a vacuum to draw the film into a suitable mold. The vacuumdrawing the film into the mold can be applied for about 0.2 to about 5seconds, or about 0.3 to about 3, or about 0.5 to about 1.5 seconds,once the film is on the horizontal portion of the surface. This vacuumcan be such that it provides an under-pressure in a range of 10 mbar to1000 mbar, or in a range of 100 mbar to 600 mbar, for example.

The molds, in which articles such as packets may be made, can have anyshape, length, width and depth, depending on the required dimensions ofthe pouches. The molds may also vary in size and shape from one toanother, if desirable. For example, the volume of the final pouches maybe about 5 ml to about 300 ml, or about 10 to 150 ml, or about 20 toabout 100 ml, and that the mold sizes are adjusted accordingly.

In one embodiment, the packet or other article comprises a first and asecond sealed compartment. The second compartment is in a generallysuperposed relationship with the first sealed compartment such that thesecond sealed compartment and the first sealed compartment share apartitioning wall interior to the pouch.

In one embodiment, the packet or other article comprising a first and asecond compartment further comprises a third sealed compartment. Thethird sealed compartment is in a generally superposed relationship withthe first sealed compartment such that the third sealed compartment andthe first sealed compartment share a partitioning wall interior to thepouch.

In some embodiments, the first composition and the second compositionare selected from one of the following combinations: liquid, liquid;liquid, powder; powder, powder; and powder, liquid.

In some embodiments, the first, second and third compositions areselected from one of the following combinations: solid, liquid, liquidand liquid, liquid, liquid.

In one embodiment, the single compartment or plurality of sealedcompartments contains a composition. The plurality of compartments mayeach contain the same or a different composition. The composition isselected from a liquid, solid or combination thereof.

In one embodiment, the composition may be selected from the group ofliquid light duty and liquid heavy duty liquid detergent compositions,powdered detergent compositions, dish detergent for hand washing and/ormachine washing; hard surface cleaning compositions, fabric enhancers,detergent gels commonly used for laundry, and bleach and laundryadditives, shampoos, and body washes.

Shaping, Sealing, and Thermoforming

A contemplated class of embodiments is characterized by goodthermoformability of the water-soluble film made as described herein. Athermoformable film is one that can be shaped through the application ofheat and a force.

Thermoforming a film is the process of heating the film, shaping it in amold, and then allowing the film to cool, whereupon the film will holdthe shape of the mold. The heat may be applied using any suitable means.For example, the film may be heated directly by passing it under aheating element or through hot air, prior to feeding it onto a surfaceor once on a surface. Alternatively, it may be heated indirectly, forexample by heating the surface or applying a hot item onto the film. Insome embodiments, the film is heated using an infrared light. The filmmay be heated to a temperature of about 50 to about 150° C., about 50 toabout 120° C., about 60 to about 130° C., about 70 to about 120° C., orabout 60 to about 90° C. Thermoforming can be performed by any one ormore of the following processes: the manual draping of a thermallysoftened film over a mold, or the pressure induced shaping of a softenedfilm to a mold (e.g., vacuum forming), or the automatic high-speedindexing of a freshly extruded sheet having an accurately knowntemperature into a forming and trimming station, or the automaticplacement, plug and/or pneumatic stretching and pressuring forming of afilm.

Alternatively, the film can be wetted by any suitable means, for exampledirectly by spraying a wetting agent (including water, a solution of thefilm composition, a plasticizer for the film composition, or anycombination of the foregoing) onto the film, prior to feeding it ontothe surface or once on the surface, or indirectly by wetting the surfaceor by applying a wet item onto the film.

Once a film has been heated and/or wetted, it may be drawn into anappropriate mold, preferably using a vacuum. The filling of the moldedfilm can be accomplished by utilizing any suitable means. In someembodiments, the most preferred method will depend on the product formand required speed of filling. In some embodiments, the molded film isfilled by in-line filling techniques. The filled, open packets are thenclosed forming the pouches, using a second film, by any suitable method.This may be accomplished while in horizontal position and in continuous,constant motion. The closing may be accomplished by continuously feedinga second film, preferably water-soluble film, over and onto the openpackets and then preferably sealing the first and second film together,typically in the area between the molds and thus between the packets.

Any suitable method of sealing the packet and/or the individualcompartments thereof may be utilized. Non-limiting examples of suchmeans include heat sealing, solvent welding, solvent or wet sealing, andcombinations thereof. Typically, only the area which is to form the sealis treated with heat or solvent. The heat or solvent can be applied byany method, typically on the closing material, and typically only on theareas which are to form the seal. If solvent or wet sealing or weldingis used, it may be preferred that heat is also applied. Preferred wet orsolvent sealing/welding methods include selectively applying solventonto the area between the molds, or on the closing material, by forexample, spraying or printing this onto these areas, and then applyingpressure onto these areas, to form the seal. Sealing rolls and belts asdescribed above (optionally also providing heat) can be used, forexample.

The formed pouches may then be cut by a cutting device. Cutting can beaccomplished using any known method. It may be preferred that thecutting is also done in continuous manner, and preferably with constantspeed and preferably while in horizontal position. The cutting devicecan, for example, be a sharp item, or a hot item, or a laser, whereby inthe latter cases, the hot item or laser ‘burns’ through the film/sealingarea.

The different compartments of a multi-compartment pouches may be madetogether in a side-by-side style wherein the resulting, cojoined pouchesmay or may not be separated by cutting. Alternatively, the compartmentscan be made separately.

In some embodiments, pouches may be made according to a processcomprising the steps of: a) forming a first compartment (as describedabove); b) forming a recess within some or all of the closed compartmentformed in step (a), to generate a second molded compartment superposedabove the first compartment; c) filling and closing the secondcompartments by means of a third film; d) sealing the first, second andthird films; and e) cutting the films to produce a multi-compartmentpouch. The recess formed in step (b) may be achieved by applying avacuum to the compartment prepared in step (a).

In some embodiments, second, and/or third compartment(s) can be made ina separate step and then combined with the first compartment asdescribed in European Patent Application Number 08101442.5 or WO2009/152031.

In some embodiments, pouches may be made according to a processcomprising the steps of: a) forming a first compartment, optionallyusing heat and/or vacuum, using a first film on a first forming machine;b) filling the first compartment with a first composition; c) on asecond forming machine, deforming a second film, optionally using heatand vacuum, to make a second and optionally third molded compartment; d)filling the second and optionally third compartments; e) sealing thesecond and optionally third compartment using a third film; f) placingthe sealed second and optionally third compartments onto the firstcompartment; g) sealing the first, second and optionally thirdcompartments; and h) cutting the films to produce a multi-compartmentpouch.

The first and second forming machines may be selected based on theirsuitability to perform the above process. In some embodiments, the firstforming machine is preferably a horizontal forming machine, and thesecond forming machine is preferably a rotary drum forming machine,preferably located above the first forming machine.

It should be understood that by the use of appropriate feed stations, itmay be possible to manufacture multi-compartment pouches incorporating anumber of different or distinctive compositions and/or different ordistinctive liquid, gel or paste compositions.

In some embodiments, the film and/or pouch is sprayed or dusted with asuitable material, such as an active agent, a lubricant, an aversiveagent, or mixtures thereof. In some embodiments, the film and/or pouchis printed upon, for example, with an ink and/or an active agent.

Pouch Contents

The present articles (e.g., in the form of pouches or packets) maycontain various compositions, for example household care compositions. Amulti-compartment pouch may contain the same or different compositionsin each separate compartment. The composition is proximal to thewater-soluble film. The composition may be less than about 10 cm, orless than about 5 cm, or less than about 1 cm from the film. Typicallythe composition is adjacent to the film or in contact with the film. Thefilm may be in the form of a pouch or a compartment, containing thecomposition therein.

As described above, the film and pouch are particularly advantageous forpackaging (e.g., in direct contact with) materials which haveexchangeable hydrogen ions, for example compositions characterized byacid/base equilibria, such as amine-fatty acid equilibria and/oramine-anionic surfactant acid equilibria.

This feature of the disclosure may be utilized to keep compositionscontaining incompatible ingredients (e.g., bleach and enzymes)physically separated or partitioned from each other. It is believed thatsuch partitioning may expand the useful life and/or decrease physicalinstability of such ingredients. Additionally or alternatively, suchpartitioning may provide aesthetic benefits as described in EuropeanPatent Application Number 09161692.0.

Non-limiting examples of useful compositions (e.g., household carecompositions) include light duty and heavy duty liquid detergentcompositions, hard surface cleaning compositions, detergent gelscommonly used for laundry, bleach and laundry additives, fabric enhancercompositions (such as fabric softeners), shampoos, body washes, andother personal care compositions. Compositions of use in the presentpouches may take the form of a liquid, solid or a powder. Liquidcompositions may comprise a solid. Solids may include powder oragglomerates, such as micro-capsules, beads, noodles or one or morepearlized balls or mixtures thereof. Such a solid element may provide atechnical benefit, through the wash or as a pre-treat, delayed orsequential release component; additionally or alternatively, it mayprovide an aesthetic effect.

The compositions encapsulated by the films described herein can have anysuitable viscosity depending on factors such as formulated ingredientsand purpose of the composition. In one embodiment, the composition has ahigh shear viscosity value, at a shear rate of 20 s⁻¹ and a temperatureof 20° C., of 100 to 3,000 cP, alternatively 300 to 2,000 cP,alternatively 500 to 1,000 cP, and a low shear viscosity value, at ashear rate of 1 s⁻¹ and a temperature of 20° C., of 500 to 100,000 cP,alternatively 1000 to 10,000 cP, alternatively 1,300 to 5,000 cP.Methods to measure viscosity are known in the art. According to thepresent invention viscosity measurements are carried out using arotational rheometer e.g. TA instruments AR550. The instrument includesa 40 mm 2° or 1° cone fixture with a gap of around 50-60 μm forisotropic liquids, or a 40 mm flat steel plate with a gap of 1000 μm forparticles containing liquids. The measurement is carried out using aflow procedure that contains a conditioning step, a peak hold and acontinuous ramp step. The conditioning step involves the setting of themeasurement temperature at 20° C., a pre-shear of 10 seconds at a shearrate of 10 s⁻¹, and an equilibration of 60 seconds at the selectedtemperature. The peak hold involves applying a shear rate of 0.05 s⁻¹ at20° C. for 3 min with sampling every 10 s. The continuous ramp step isperformed at a shear rate from 0.1 to 1200 s⁻¹ for 3 min at 20° C. toobtain the full flow profile.

In pouches or other articles comprising laundry, laundry additive and/orfabric enhancer compositions, the compositions may comprise one or moreof the following non-limiting list of ingredients: fabric care benefitagent; detersive enzyme; deposition aid; rheology modifier; builder;bleach; bleaching agent; bleach precursor; bleach booster; bleachcatalyst; perfume and/or perfume microcapsules (see for example U.S.Pat. No. 5,137,646); perfume loaded zeolite; starch encapsulated accord;polyglycerol esters; whitening agent; pearlescent agent; enzymestabilizing systems; scavenging agents including fixing agents foranionic dyes, complexing agents for anionic surfactants, and mixturesthereof; optical brighteners or fluorescers; polymer including but notlimited to soil release polymer and/or soil suspension polymer;dispersants; antifoam agents; non-aqueous solvent; fatty acid; sudssuppressors, e.g., silicone suds suppressors (see: U.S. Publication No.2003/0060390 A1, ¶65-77); cationic starches (see: US 2004/0204337 A1 andUS 2007/0219111 A1); scum dispersants (see: US 2003/0126282 A1, ¶89-90);substantive dyes; hueing dyes (see: US 2014/0162929A1); colorants;opacifier; antioxidant; hydrotropes such as toluenesulfonates,cumenesulfonates and naphthalenesulfonates; color speckles; coloredbeads, spheres or extrudates; clay softening agents; anti-bacterialagents. Any one or more of these ingredients is further described indescribed in European Patent Application Number 09161692.0, U.S.Publication Number 2003/0139312A1 and U.S. Patent Application No.61/229,981. Additionally or alternatively, the compositions may comprisesurfactants, quaternary ammonium compounds, and/or solvent systems.Quaternary ammonium compounds may be present in fabric enhancercompositions, such as fabric softeners, and comprise quaternary ammoniumcations that are positively charged polyatomic ions of the structure NR₄⁺, where R is an alkyl group or an aryl group.

Surfactants

The detergent compositions can comprise from about 1% to 80% by weightof a surfactant. Surfactant is particularly preferred as a component ofthe first composition. Preferably, the first composition comprises fromabout 5% to 50% by weight of surfactant. The second and thirdcompositions may comprise surfactant at levels of from 0.1 to 99.9%.

Detersive surfactants utilized can be of the anionic, nonionic,zwitterionic, ampholytic or cationic type or can comprise compatiblemixtures of these types. More preferably surfactants are selected fromthe group consisting of anionic, nonionic, cationic surfactants andmixtures thereof. Preferably the compositions are substantially free ofbetaine surfactants. Detergent surfactants useful herein are describedin U.S. Pat. Nos. 3,664,961; 3,919,678; 4,222,905; and 4,239,659.Anionic and nonionic surfactants are preferred.

Useful anionic surfactants can themselves be of several different types.For example, water-soluble salts of the higher fatty acids, i.e.,“soaps”, are useful anionic surfactants in the compositions herein. Thisincludes alkali metal soaps such as the sodium, potassium, ammonium, andalkyl ammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms, and preferably from about 12 to about 18 carbonatoms. Soaps can be made by direct saponification of fats and oils or bythe neutralization of free fatty acids. Particularly useful are thesodium and potassium salts of the mixtures of fatty acids derived fromcoconut oil and tallow, i.e., sodium or potassium tallow and coconutsoap.

Additional non-soap anionic surfactants which are suitable for useherein include the water-soluble salts, preferably the alkali metal, andammonium salts, of organic sulfuric reaction products having in theirmolecular structure an alkyl group containing from about 10 to about 20carbon atoms and a sulfonic acid or sulfuric acid ester group. (Includedin the term “alkyl” is the alkyl portion of acyl groups.) Examples ofthis group of synthetic surfactants include: a) the sodium, potassiumand ammonium alkyl sulfates, especially those obtained by sulfating thehigher alcohols (C₈-C₁₈) such as those produced by reducing theglycerides of tallow or coconut oil; b) the sodium, potassium andammonium alkyl polyethoxylate sulfates, particularly those in which thealkyl group contains from 10 to 22, preferably from 12 to 18 carbonatoms, and wherein the polyethoxylate chain contains from 1 to 15,preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassiumalkylbenzene sulfonates in which the alkyl group contains from about 9to about 15 carbon atoms, in straight chain or branched chainconfiguration, e.g., those of the type described in U.S. Pat. Nos.2,220,099 and 2,477,383. Especially valuable are linear straight chainalkylbenzene sulfonates in which the average number of carbon atoms inthe alkyl group is from about 11 to 13, abbreviated as C₁₁-C₁₃ LAS.

Anionic surfactants of the present invention and adjunct anioniccosurfactants, may exist in an acid form, and said acid form may beneutralized to form a surfactant salt which is desirable for use in thepresent detergent compositions. Typical agents for neutralizationinclude the metal counterion base such as hydroxides, e.g., NaOH or KOH.Further preferred agents for neutralizing anionic surfactants of thepresent invention and adjunct anionic surfactants or cosurfactants intheir acid forms include ammonia, amines, or alkanolamines.Alkanolamines are preferred. Suitable non-limiting examples includingmonoethanolamine, diethanolamine, triethanolamine, and other linear orbranched alkanolamines known in the art; for example, highly preferredalkanolamines include 2-amino-1-propanol, 1-aminopropanol,monoisopropanolamine, or 1-amino-3-propanol. Amine neutralization may bedone to a full or partial extent, e.g. part of the anionic surfactantmix may be neutralized with sodium or potassium and part of the anionicsurfactant mix may be neutralized with amines or alkanolamines.

Preferred nonionic surfactants are those of the formula R₁(OC₂H₄)_(n)OH,wherein R₁ is a C₁₀-C₁₆ alkyl group or a C₈-C₁₂ alkyl phenyl group, andn is from 3 to about 80. Particularly preferred are condensationproducts of C₁₂-C₁₅ alcohols with from about 5 to about 20 moles ofethylene oxide per mole of alcohol, e.g., C₁₂-C₁₃ alcohol condensed withabout 6.5 moles of ethylene oxide per mole of alcohol.

Solvent System

The solvent system in the present compositions can be a solvent systemcontaining water alone or mixtures of organic solvents with water.Preferred organic solvents include glycerol, ethylene glycol, 1,3propanediol, 1,2 propanediol, tetramethylene glycol, pentamethyleneglycol, hexamethylene glycol, 2,3-butane diol, 1,3 butanediol,diethylene glycol, triethylene glycol, polyethylene glycol, glycerolformal dipropylene glycol, polypropylene glycol, dipropylene glycoln-butyl ether, and mixtures thereof, more preferably 1,2-propanediol,ethanol, glycerol, dipropylene glycol, methyl propane diol and mixturesthereof. Other lower alcohols, C₁-C₄ alkanolamines such asmonoethanolamine and triethanolamine, can also be used. Solvent systemscan be absent, for example from anhydrous solid embodiments of thedisclosure, but more typically are present at levels in the range offrom about 0.1% to about 98%, preferably at least about 1% to about 50%,more usually from about 5% to about 25%. Typically, the presentcompositions, particularly when in liquid form, comprise less than 50%water, preferably from about 0.1% to about 20% water, or more preferablyfrom about 0.5% to about 15%, or from about 5% to about 12%, by weightof the composition, of water.

The compositions herein can generally be prepared by mixing theingredients together. If a pearlescent material is used it should beadded in the late stages of mixing. If a rheology modifier is used, itis preferred to first form a pre-mix within which the rheology modifieris dispersed in a portion of the water and optionally other ingredientseventually used to comprise the compositions. This pre-mix is formed insuch a way that it forms a structured liquid. To this structured pre-mixcan then be added, while the pre-mix is under agitation, thesurfactant(s) and essential laundry adjunct materials, along with waterand whatever optional detergent composition adjuncts are to be used.

The pH of the useful compositions may be from about 2 to about 12, about4 to about 12, about 5.5 to about 9.5, about 6 to about 8.5, or about6.5 to about 8.2. Laundry detergent compositions may have a pH of about6 to about 10, about 6.5 to about 8.5, about 7 to about 7.5, or about 8to about 10. Auto-dishwashing compositions may have a pH of about 8 toabout 12. Laundry detergent additive compositions may have a pH of about4 to about 8. Fabric enhancers may have a pH of from about 2 or 4 toabout 8, or from about 2 to about 4, or from about 2.5 to about 3.5, orfrom about 2.7 to about 3.3.

The pH of the detergent is defined as the pH of an aqueous 10%(weight/volume) solution of the detergent at 20±2° C.; for solids andpowdered detergent this is defined as the pH of an aqueous 1%(weight/volume) solution of the detergent at 20±2° C. Any meter capableof measuring pH to ±0.01 pH units is suitable. Orion meters (ThermoScientific, Clintinpark—Keppekouter, Ninovesteenweg 198, 9320Erembodegem—Aalst, Belgium) or equivalent are acceptable instruments.The pH meter should be equipped with a suitable glass electrode withcalomel or silver/silver chloride reference. An example includes MettlerDB 115. The electrode shall be stored in the manufacturer's recommendedelectrolyte solution.

The 10% aqueous solution of the detergent is prepared according to thefollowing procedure. A sample of 10±0.05 grams is weighted with abalance capable of accurately measuring to ±0.02 grams. The sample istransferred to a 100 mL volumetric flask, diluted to volume withpurified water (deionized and/or distilled water are suitable as long asthe conductivity of the water is <5 μS/cm), and thoroughly mixed. About50 mL of the resulting solution is poured into a beaker, the temperatureis adjusted to 20±2° C. and the pH is measured according to the standardprocedure of the pH meter manufacturer (it is critical to follow themanufacturer's instructions to also set up and calibrate the pHassembly).

For solid and powdered detergents, the 1% aqueous solution of thedetergent is prepared according to the following procedure. A sample of10±0.05 grams is weighted with a balance capable of accurately measuringto ±0.02 grams. The sample is transferred to a volumetric flask of 1000mL, diluted to volume with purified water (deionized and/or distilledwater are suitable as long as the conductivity of the water is <5μS/cm), and thoroughly mixed. About 50 mL of the resulting solution ispoured into a beaker, the temperature is adjusted to 20±2° C. and the pHis measured according to the standard procedure of the pH metermanufacturer (it is critical to follow the manufacturer's instructionsto also set up and calibrate the pH assembly).

Bleaches

Inorganic and organic bleaches are suitable cleaning actives for useherein. Inorganic bleaches include perhydrate salts such as perborate,percarbonate, perphosphate, persulfate and persilicate salts. Theinorganic perhydrate salts are normally the alkali metal salts. Theinorganic perhydrate salt may be included as the crystalline solidwithout additional protection. Alternatively, the salt can be coated asis known in the art.

Alkali metal percarbonates, particularly sodium percarbonate arepreferred perhydrates for use in the detergent composition describedherein. The percarbonate is most preferably incorporated into theproducts in a coated form which provides in-product stability. Asuitable coating material providing in product stability comprises mixedsalt of a water-soluble alkali metal sulphate and carbonate. Suchcoatings together with coating processes have previously been describedin GB1,466,799, and U.S. Pat. Nos. 3,975,280; 4,075,116; and 5,340,496,each incorporated herein by reference. The weight ratio of the mixedsalt coating material to percarbonate lies in the range from 1:99 to1:9, and preferably from 1:49 to 1:19. Preferably, the mixed salt is ofsodium sulphate and sodium carbonate which has the general formulaNa₂SO₄.n.Na₂CO₃ wherein n is from 0.1 to 3, preferably from 0.3 to 1.0,and more preferably from 0.2 to 0.5. Another suitable coating materialproviding in product stability comprises sodium silicate of SiO₂:Na₂Oratio from 1.8:1 to 3.0:1, preferably 1.8:1 to 2.4:1, and/or sodiummetasilicate, preferably applied at a level of from 2% to 10%, (normallyfrom 3% to 5%) of SiO₂ by weight of the inorganic perhydrate salt, suchas potassium peroxymonopersulfate. Other coatings which containmagnesium silicate, silicate and borate salts, silicate and boric acids,waxes, oils, and fatty soaps can also be used advantageously

Organic bleaches can include organic peroxyacids including diacyl andtetraacylperoxides, especially diperoxydodecanedioc acid,diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid. Dibenzoylperoxide is a preferred organic peroxyacid herein. The diacyl peroxide,especially dibenzoyl peroxide, preferably can be present in the form ofparticles having a weight average diameter of from about 0.1 to about100 microns, preferably from about 0.5 to about 30 microns, morepreferably from about 1 to about 10 microns. Preferably, at least about25% to 100%, more preferably at least about 50%, even more preferably atleast about 75%, most preferably at least about 90%, of the particlesare smaller than 10 microns, preferably smaller than 6 microns.

Other organic bleaches include the peroxy acids, particular examplesbeing the alkylperoxy acids and the arylperoxy acids. Preferredrepresentatives are: (a) peroxybenzoic acid and its ring-substitutedderivatives, such as alkylperoxybenzoic acids, but alsoperoxy-α-naphthoic acid and magnesium monoperphthalate; (b) thealiphatic or substituted aliphatic peroxy acids, such as peroxylauricacid, peroxystearic acid, ε-phthalimidoperoxycaproicacid[phthaloiminoperoxyhexanoic acid (PAP)],o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid andN-nonenylamidopersuccinates; and (c) aliphatic and araliphaticperoxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid,1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid,the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid,N,N-terephthaloyldi(6-aminopercaproic acid)

Bleach activators can include organic peracid precursors that enhancethe bleaching action in the course of cleaning at temperatures of 60° C.and below. Bleach activators suitable for use herein include compoundswhich, under perhydrolysis conditions, give aliphatic peroxoycarboxylicacids having preferably from 1 to 10 carbon atoms, in particular from 2to 4 carbon atoms, and/or optionally substituted perbenzoic acid.Suitable substances bear O-acyl and/or N-acyl groups of the number ofcarbon atoms specified and/or optionally substituted benzoyl groups.Preference is given to polyacylated alkylenediamines, in particulartetraacetylethylenediamine (TAED), acylated triazine derivatives, inparticular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),acylated glycolurils, in particular tetraacetylglycoluril (TAGU),N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylatedphenolsulfonates, in particular n-nonanoyl- orisononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides,in particular phthalic anhydride, acylated polyhydric alcohols, inparticular triacetin, ethylene glycol diacetate and2,5-diacetoxy-2,5-dihydrofuran and also triethylacetyl citrate (TEAC).

Bleach catalysts preferred for use in the detergent composition hereininclude the manganese triazacyclononane and related complexes (U.S. Pat.Nos. 4,246,612, 5,227,084); Co, Cu, Mn and Fe bispyridylamine andrelated complexes (U.S. Pat. No. 5,114,611); and pentamine acetatecobalt(III) and related complexes (U.S. Pat. No. 4,810,410). A completedescription of bleach catalysts suitable for use herein can be found inU.S. Pat. No. 6,599,871, incorporated herein by reference.

Dishwashing Agents

A preferred surfactant for use in automatic dishwashing detergents islow foaming by itself or in combination with other components (e.g. sudssuppressers). Preferred for use herein are low and high cloud pointnonionic surfactants and mixtures thereof including nonionic alkoxylatedsurfactants (especially ethoxylates derived from C₆-C₁₈ primaryalcohols), ethoxylated-propoxylated alcohols (e.g., Olin Corporation'sPOLY-TERGENT® SLF18), epoxy-capped poly(oxyalkylated) alcohols (e.g.,Olin Corporation's POLY-TERGENT® SLF18B—see WO-A-94/22800), ether-cappedpoly(oxyalkylated) alcohol surfactants, and blockpolyoxyethylene-polyoxypropylene polymeric compounds such as PLURONIC®,REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp.,Wyandotte, Mich.; amphoteric surfactants such as the C₁₂-C₂₀ alkyl amineoxides (preferred amine oxides for use herein include lauryldimethylamine oxide and hexadecyl dimethyl amine oxide), and alkylamphocarboxylic surfactants such as MIRANOL™ C2M; and zwitterionicsurfactants such as the betaines and sultaines; and mixtures thereof.Surfactants suitable for use herein are disclosed, for example, in U.S.Pat. Nos. 3,929,678, 4,259,217, EP-A-0414 549, WO-A-93/08876 andWO-A-93/08874. Surfactants can be present at a level of from about 0.2%to about 30% by weight, more preferably from about 0.5% to about 10% byweight, most preferably from about 1% to about 5% by weight of adetergent composition.

Other Compositions and Additives

Builders suitable for use in the detergent composition described hereininclude water-soluble builders, including citrates, carbonates, silicateand polyphosphates, e.g. sodium tripolyphosphate and sodiumtripolyphosphate hexahydrate, potassium tripolyphosphate and mixedsodium and potassium tripolyphosphate salts.

The household care composition may comprise an enzyme. Examples ofsuitable enzymes include, but are not limited to, hemicellulases,peroxidases, proteases, cellulases, xylanases, lipases, phospholipases,esterases, cutinases, pectinases, mannanases, pectate lyases,keratinases, reductases, oxidases, phenoloxidases, lipoxygenases,ligninases, pullulanases, tannases, pentosanases, malanases,ß-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase,and amylases, or mixtures thereof. A typical combination is an enzymecocktail that may comprise, for example, a protease and lipase inconjunction with amylase. When present in a household care composition,the aforementioned additional enzymes may be present at levels fromabout 0.00001% to about 2%, from about 0.0001% to about 1% or even fromabout 0.001% to about 0.5% enzyme protein by weight of the composition.

Enzymes suitable for use in the detergent composition described hereininclude bacterial and fungal cellulases including CAREZYME and CELLUZYME(Novo Nordisk A/S); peroxidases; lipases including AMANO-P (AmanoPharmaceutical Co.), M1 LIPASE and LIPOMAX (Gist-Brocades) and LIPOLASEand LIPOLASE ULTRA (Novo); cutinases; proteases including ESPERASE,ALCALASE, DURAZYM and SAVINASE (Novo) and MAXATASE, MAXACAL, PROPERASEand MAXAPEM (Gist-Brocades); α and β amylases including PURAFECT OX AM(Genencor) and TERMAMYL, BAN, FUNGAMYL, DURAMYL, and NATALASE (Novo);pectinases; and mixtures thereof. Enzymes can be added herein as prills,granulates, or cogranulates at levels typically in the range from about0.0001% to about 2% pure enzyme by weight of the cleaning composition.

Enzymes for use in household care compositions can be stabilized byvarious techniques. The enzymes employed herein can be stabilized by thepresence of water-soluble sources of calcium and/or magnesium ions inthe finished fabric and home care products that provide such ions to theenzymes. In case of aqueous consumer products comprising protease, areversible protease inhibitor, such as peptide aldehydes or a boroncompound including borate, 4-formyl phenylboronic acid, phenylboronicacid and derivatives thereof, or compounds such as calcium formate,sodium formate and 1,2-propane diol can be added to further improvestability.

The composition may comprise a fabric hueing agent. Suitable fabrichueing agents include dyes, dye-clay conjugates, and pigments. Suitabledyes include small molecule dyes and polymeric dyes. Suitable smallmolecule dyes include small molecule dyes selected from the groupconsisting of dyes falling into the Colour Index (C.I.) classificationsof Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, AcidViolet, Basic Blue, Basic Violet and Basic Red, or mixtures thereof.Preferred dyes include alkoxylated azothiophenes, Solvent Violet 13,Acid Violet 50 and Direct Violet 9.

The composition may comprise an encapsulate. In one aspect, anencapsulate comprising a core, a shell having an inner and outersurface, said shell encapsulating said core. The core may compriseperfume. The shell may comprise melamine formaldehyde and/or crosslinked melamine formaldehyde. The shell may comprise a polyacrylatepolymer.

Suitable encapsulates may comprise a core material and a shell, saidshell at least partially surrounding said core material. At least 75%,85% or even 90% of said encapsulates may have a fracture strength offrom about 0.2 MPa to about 10 MPa, from about 0.4 MPa to about 5 MPa,from about 0.6 MPa to about 3.5 MPa, or even from about 0.7 MPa to about3 MPa; and a benefit agent leakage of from 0% to about 30%, from 0% toabout 20%, or even from 0% to about 5%. In one aspect, at least 75%, 85%or even 90% of said encapsulates may have a particle size of from about1 microns to about 80 microns, about 5 microns to 60 microns, from about10 microns to about 50 microns, or even from about 15 microns to about40 microns. In one aspect, at least 75%, 85% or even 90% of saidencapsulates may have a particle wall thickness of from about 30 nm toabout 250 nm, from about 80 nm to about 180 nm, or even from about 100nm to about 160 nm.

In one aspect, said encapsulates' core material may comprise a materialselected from the group consisting of a perfume raw material and/oroptionally a material selected from the group consisting of vegetableoil, including neat and/or blended vegetable oils including castor oil,coconut oil, cottonseed oil, grape oil, rapeseed, soybean oil, corn oil,palm oil, linseed oil, safflower oil, olive oil, peanut oil, coconutoil, palm kernel oil, castor oil, lemon oil and mixtures thereof; estersof vegetable oils, esters, including dibutyl adipate, dibutyl phthalate,butyl benzyl adipate, benzyl octyl adipate, tricresyl phosphate,trioctyl phosphate and mixtures thereof; straight or branched chainhydrocarbons, including those straight or branched chain hydrocarbonshaving a boiling point of greater than about 80° C.; partiallyhydrogenated terphenyls, dialkyl phthalates, alkyl biphenyls, includingmonoisopropylbiphenyl, alkylated naphthalene, includingdipropylnaphthalene, petroleum spirits, including kerosene, mineral oiland mixtures thereof; aromatic solvents, including benzene, toluene andmixtures thereof; silicone oils; and mixtures thereof.

The composition can also comprise a deposition aid, preferablyconsisting of the group comprising cationic or nonionic polymers.Suitable polymers include cationic starches, cationichydroxyethylcellulose, polyvinylformaldehyde, locust bean gum, mannans,xyloglucans, tamarind gum, polyethyleneterephthalate and polymerscontaining dimethylaminoethyl methacrylate, optionally with one ormonomers selected from the group comprising acrylic acid and acrylamide.

Suds suppressers suitable for use in the detergent composition describedherein include nonionic surfactants having a low cloud point. “Cloudpoint” as used herein, is a well known property of nonionic surfactantswhich is the result of the surfactant becoming less soluble withincreasing temperature, the temperature at which the appearance of asecond phase is observable is referred to as the “cloud point.” As usedherein, a “low cloud point” nonionic surfactant is defined as a nonionicsurfactant system ingredient having a cloud point of less than 30° C.,preferably less than about 20° C., and even more preferably less thanabout 10° C., and most preferably less than about 7.5° C. Low cloudpoint nonionic surfactants can include nonionic alkoxylated surfactants,especially ethoxylates derived from primary alcohol, andpolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverseblock polymers. Also, such low cloud point nonionic surfactants caninclude, for example, ethoxylated-propoxylated alcohol (e.g., BASFPOLY-TERGENT SLF18) and epoxy-capped poly(oxyalkylated) alcohols (e.g.,BASF POLY-TERGENT SLF18B series of nonionics, as described, for example,in U.S. Pat. No. 5,576,281).

Other suitable components for use in the detergent or household carecomposition described herein include cleaning polymers havinganti-redeposition, soil release or other detergency properties.Anti-redeposition polymers for use herein include acrylic acidcontaining polymers such as SOKALAN PA30, PA20, PA15, PA10 and SOKALANCP10 (BASF GmbH), ACUSOL 45N, 480N, 460N (Rohm and Haas), acrylicacid/maleic acid copolymers such as SOKALAN CP5, and acrylic/methacryliccopolymers. The household care composition may comprise amphiphilicalkoxylated grease cleaning polymers which have balanced hydrophilic andhydrophobic properties such that they remove grease particles fromfabrics and surfaces. Specific embodiments of the amphiphilicalkoxylated grease cleaning polymers of the present invention comprise acore structure and a plurality of alkoxylate groups attached to thatcore structure. Suitable polymers include amine-based polymers such asalkoxylated polyalkyleneimines (e.g., PEI600 EO20 and/or ethoxysulfatedhexamethylene diamine dimethyl quats), which, optionally, may bequaternized. Other polymers include alkoxylated polyalkylenimines thathave an inner polyethylene oxide block and an outer polypropylene oxideblock. Other suitable polymers include amine-based polymers such asalkoxylated polyalkyleneimines (e.g., PEI600 EO20 and/or ethoxysulfatedhexamethylene diamine dimethyl quats), which, optionally, may bequaternized. Soil release polymers for use herein include alkyl andhydroxyalkyl celluloses (U.S. Pat. No. 4,000,093), polyoxyethylenes,polyoxypropylenes and copolymers thereof, and nonionic and anionicpolymers based on terephthalate esters of ethylene glycol, propyleneglycol and mixtures thereof.

Structured liquids can either be internally structured, whereby thestructure is formed by primary ingredients (e.g. surfactant material)and/or externally structured by providing a three dimensional matrixstructure using secondary ingredients (e.g. polymers, clay and/orsilicate material). The composition may comprise a structurant,preferably from 0.01 wt % to 5 wt %, from 0.1 wt % to 2.0 wt %structurant. The structurant is typically selected from the groupconsisting of diglycerides and triglycerides, ethylene glycoldistearate, microcrystalline cellulose, cellulose-based materials,microfiber cellulose, hydrophobically modified alkali-swellableemulsions such as Polygel W30 (3VSigma), biopolymers, xanthan gum,gellan gum, and mixtures thereof. A suitable structurant includeshydrogenated castor oil, and non-ethoxylated derivatives thereof. Asuitable structurant is disclosed in U.S. Pat. No. 6,855,680. Suchstructurants have a thread-like structuring system having a range ofaspect ratios. Other suitable structurants and the processes for makingthem are described in WO2010/034736.

Heavy metal sequestrants and crystal growth inhibitors are also suitablefor use in the detergent, for example diethylenetriamine penta(methylenephosphonate), ethylenediamine tetra(methylene phosphonate)hexamethylenediamine tetra(methylene phosphonate), ethylenediphosphonate, hydroxy-ethylene-1,1-diphosphonate, nitrilotriacetate,ethylenediaminotetracetate, ethylenediamine-N,N′-disuccinate in theirsalt and free acid forms.

Suitable for use in the detergent composition described herein is also acorrosion inhibitor, for example organic silver coating agents(especially paraffins such as WINOG 70 sold by Wintershall, Salzbergen,Germany), nitrogen-containing corrosion inhibitor compounds (for examplebenzotriazole and benzimadazole—see GB-A-1137741) and Mn(II) compounds,particularly Mn(II) salts of organic ligands.

Other suitable components for use in the detergent composition hereininclude enzyme stabilizers, for example calcium ion, boric acid andpropylene glycol.

Suitable rinse additives are known in the art. Commercial rinse aids fordishwashing typically are mixtures of low-foaming fatty alcoholpolyethylene/polypropylene glycol ethers, solubilizers (for examplecumene sulfonate), organic acids (for example citric acid) and solvents(for example ethanol). The function of such rinse aids is to influencethe interfacial tension of the water in such a way that it is able todrain from the rinsed surfaces in the form of a thin coherent film, sothat no water droplets, streaks, or films are left after the subsequentdrying process. European Patent 0 197 434 B1 describes rinse aids whichcontain mixed ethers as surfactants. Rinse additives such as fabricsofteners and the like are also contemplated and suitable forencapsulation in a film according to the disclosure herein.

Methods of Use

The films and articles described herein, as well as compositionscontained therein, may be used to treat a substrate, e.g., fabric or ahard surface, for example by contacting the substrate with the film,article, and/or composition contained therein. The contacting step mayoccur manually or in an automatic machine, e.g., an automatic (top orfront-loading) laundry machine or an automatic dishwashing machine. Thecontacting step may occur in the presence of water, which may be at atemperature up to about 80° C., or up to about 60° C., or up to about40° C., or up to about 30° C., or up to about 20° C., or up to about 15°C., or up to about 10° C., or up to about 5° C. As noted above, thepresent films and articles made therefrom are particularly suited forcold water dissolution and therefore provide benefits in cold-waterwashes (e.g., from about 1° C. to about 30° C., or from about 5° C. toabout 20° C.). The contacting step may be followed by a multi-rinsecycle or even by a single rinse cycle; because the film has gooddissolution properties, less water is required to dissolve the filmand/or release the contents contained therein.

Specific contemplated aspects of the disclosure are herein described inthe following numbered paragraphs.

1. A water-soluble film comprising: a polyvinyl alcohol (PVOH) resinblend comprising: a first PVOH copolymer comprising an anionic monomerunit, the first PVOH copolymer having a first 4% solution viscosity at20° C. (μ₁); and a second PVOH polymer consisting essentially of vinylalcohol monomer units and optionally vinyl acetate monomer units, thesecond PVOH polymer having a second 4% solution viscosity at 20° C.(μ₂); wherein: an absolute viscosity difference |μ₂−μ₁| for the firstPVOH copolymer and the second PVOH polymer is in a range of 0 cP toabout 10 cP, and the first PVOH copolymer is present in an amount in arange of about 30 wt. % to about 90 wt. % of total PVOH polymers andPVOH copolymers in the film.

2. The water-soluble film of paragraph 1, wherein the second PVOHpolymer is present in an amount in a range of about 10 wt. % to about 70wt. % of total PVOH polymers and PVOH copolymers in the film.

3. The water-soluble film of any of paragraphs 1 or 2, wherein theanionic monomer unit is present in the film in an amount in a range ofabout 1.0 mol. % to about 4.2 mol. % of total PVOH polymers and PVOHcopolymers in the film.

4. A water-soluble film comprising: a polyvinyl alcohol (PVOH) resinblend comprising: a first PVOH copolymer comprising an anionic monomerunit, the first PVOH copolymer having a first 4% solution viscosity at20° C. (μ₁); and a second PVOH polymer consisting essentially of vinylalcohol monomer units and optionally vinyl acetate monomer units, thesecond PVOH polymer having a second 4% solution viscosity at 20° C.(μ₂); wherein: an absolute viscosity difference |μ₂−μ₁| for the firstPVOH copolymer and the second PVOH polymer is in a range of 0 cP toabout 10 cP, and the anionic monomer unit is present in the film in anamount in a range of about 1.0 mol. % to about 4.2 mol. % of total PVOHpolymers and PVOH copolymers in the film.

5. The water-soluble film of any of the preceding paragraphs, whereinthe anionic monomer is selected from the group consisting of vinylacetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethylmaleate, dimethyl maleate, maleic anyhydride, fumaric acid, monoalkylfumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate,fumaric anyhydride, itaconic acid, monomethyl itaconate, dimethylitaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid,ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts of the foregoing, esters of the foregoing, andcombinations thereof.

6. The water-soluble film of any of the preceding paragraphs, whereinthe anionic monomer is selected from the group consisting of acrylamidomethylpropanesulfonic acids, alkali metal salts thereof, andcombinations thereof.

7. The water-soluble film of any of the preceding paragraphs, whereinthe anionic monomer is selected from the group consisting of monomethylmaleate, alkali metal salts thereof, and combinations thereof.

8. The water-soluble film of any of the preceding paragraphs, whereinthe anionic monomer unit is present in first PVOH copolymer in an amountin a range of about 2 mol. % to about 10 mol. %.

9. The water-soluble film of paragraph 8, wherein the anionic monomerunit is present in first PVOH copolymer in an amount in a range of about5 mol. % to about 10 mol. %.

10. The water-soluble film of paragraph 9, wherein the anionic monomerunit is present in an amount in a range of about 3 mol. % to about 4.2mol. % of total PVOH polymers and PVOH copolymers in the film.

11. The water-soluble film of any of the preceding paragraphs, whereinthe PVOH resin blend consists essentially of the first PVOH copolymerand the second PVOH polymer.

12. The water-soluble film of any of the preceding paragraphs, wherein aviscosity difference (μ₂−μ₁) for the first PVOH copolymer and the secondPVOH polymer is in a range from about 0 cP to about 10 cP.

13. The water-soluble film of any of the preceding paragraphs, whereinthe first viscosity μ₁ is in a range of about 4 cP to about 24 cP.

14. The water-soluble film of any of the preceding paragraphs, whereinthe second viscosity μ₂ is in a range of about 4 cP to about 24 cP.

15. The water-soluble film of any of the preceding paragraphs, whereinthe water-soluble film has a residue value of about 45 wt. % or less asmeasured by the Dissolution Chamber Test.

16. The water-soluble film of any of the preceding paragraphs, whereinthe first PVOH copolymer and the second PVOH polymer each independentlyhave a degree of hydrolysis in a range of about 75% to about 99%.

17. The water-soluble film of any of the preceding paragraphs, whereinthe PVOH resin blend comprises a third PVOH polymer.

18. The water-soluble film of any of the preceding paragraphs, whereinthe water-soluble film further comprises at least a third water-solublepolymer which is other than a PVOH polymer.

19. The water-soluble film of paragraph 18, wherein the water-solublepolymer is selected from the group consisting of polyethyleneimines,polyvinyl pyrrolidones, polyalkylene oxides, polyacrylamides, celluloseethers, cellulose esters, cellulose amides, polyvinyl acetates,polyamides, gelatines, methylcelluloses, carboxymethylcelluloses andsalts thereof, dextrins, ethylcelluloses, hydroxyethyl celluloses,hydroxypropyl methylcelluloses, maltodextrins, starches, modifiedstarches, guar gum, gum Acacia, xanthan gum, carrageenan, polyacrylatesand salts thereof, copolymers thereof, blends thereof, and combinationsthereof.

20. The water-soluble film of any of the preceding paragraphs, whereinthe water-soluble film further comprises one or more components selectedfrom the group consisting of plasticizers, plasticizer compatibilizers,lubricants, release agents, fillers, extenders, cross-linking agents,antiblocking agents, antioxidants, detackifying agents, antifoams,nanoparticles, bleaching agents, surfactants, and combinations thereof.

21. The water-soluble film of any of the preceding paragraphs, whereinthe water-soluble film further comprises one or more plasticizers in anamount in a range of about 1 wt. % to about 40 wt. % of the film.

22. A water-soluble film comprising: a polyvinyl alcohol (PVOH) resinblend comprising: a first PVOH copolymer comprising an anionic monomerunit, the first PVOH copolymer having a first 4% solution viscosity at20° C. (μ₁); and a second PVOH polymer consisting essentially of vinylalcohol monomer units and optionally vinyl acetate monomer units, thesecond PVOH polymer having a second 4% solution viscosity at 20° C. (μ₂)of about 20 cP or less; wherein: the first PVOH copolymer is present inan amount in a range of about 30 wt. % to about 90 wt. % of total PVOHpolymers and copolymers in the film (e.g., where the water-soluble filmor component thereof can incorporate any of the refinements from thepreceding paragraphs).

23. A water-soluble film comprising: a polyvinyl alcohol (PVOH) resinblend comprising: a first PVOH copolymer comprising an anionic monomerunit, the first PVOH copolymer having a first 4% solution viscosity at20° C. (μ₁); and a second PVOH polymer consisting essentially of vinylalcohol monomer units and optionally vinyl acetate monomer units, thesecond PVOH polymer having a second 4% solution viscosity at 20° C. (μ₂)of about 20 cP or less; wherein: the anionic monomer unit is present inthe film in an amount in a range of about 1.0 mol. % to about 4.2 mol. %of total PVOH polymers and PVOH copolymers in the film (e.g., where thewater-soluble film or component thereof can incorporate any of therefinements from the preceding paragraphs).

24. A water-soluble film comprising: a polyvinyl alcohol (PVOH) resinblend comprising: a first PVOH copolymer comprising a first anionicmonomer unit; and a second PVOH polymer consisting essentially of vinylalcohol monomer units and optionally vinyl acetate monomer units;wherein the first PVOH copolymer is present in an amount in a range ofabout 30 wt. % to about 70 wt. % of total PVOH polymers and PVOHcopolymers in the film.

25. The water-soluble film of paragraph 24, wherein the second PVOHpolymer is present in an amount in a range of about 30 wt. % to about 70wt. % of total PVOH polymers and PVOH copolymers in the film.

26. The water-soluble film of paragraph 24 or 25, wherein the firstanionic monomer is selected from the group consisting of vinyl aceticacid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethylmaleate, dimethyl maleate, maleic anyhydride, fumaric acid, monoalkylfumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate,fumaric anyhydride, itaconic acid, monomethyl itaconate, dimethylitaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid,ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts of the foregoing, esters of the foregoing, andcombinations thereof.

27. The water-soluble film of any of paragraphs 24 to 26, wherein thefirst anionic monomer is selected from the group consisting ofacrylamido methylpropanesulfonic acids, alkali metal salts thereof, andcombinations thereof.

28. The water-soluble film of any of paragraphs 24 to 27, wherein thefirst anionic monomer is present in an amount less than about 3 mol. %of total PVOH polymers and PVOH copolymers in the film.

29. The water-soluble film of any of paragraphs 24 to 28, wherein thefirst PVOH copolymer and the second PVOH polymer have 4% solutionviscosity values at 20° C. that are within about 10 cP of each other.

30. The water-soluble film of any of paragraphs 24 to 29, wherein thefirst PVOH copolymer and the second PVOH polymer have 4% solutionviscosity values at 20° C. that are more than about 10 cP apart fromeach other.

31. The water-soluble film of any of paragraphs 24 to 30, wherein: thefirst PVOH copolymer has a level of incorporation of the first anionicmonomer unit in a range of about 3 mol. % to about 5 mol. %; the firstanionic monomer is selected from the group consisting of acrylamidomethylpropanesulfonic acids, alkali metal salts thereof, andcombinations thereof; the first anionic monomer is present in an amountin a range of about 1 mol. % to about 3 mol. % of total PVOH polymersand PVOH copolymers in the film; the first PVOH copolymer is present inan amount in a range from about 40 wt. % to about 60 wt. % of total PVOHpolymers and PVOH copolymers in the film; the second PVOH polymer has a4% solution viscosity value at 20° C. in a range of about 8 cP to about16 cP; and the second PVOH polymer is present in an amount in a rangefrom about 40 wt. % to about 60 wt. % of total PVOH polymers and PVOHcopolymers in the film.

32. The water-soluble film of any of paragraphs 24 to 30, wherein: thefirst PVOH copolymer has a level of incorporation of the first anionicmonomer unit in a range of about 3 mol. % to about 5 mol. %; the firstanionic monomer is selected from the group consisting of acrylamidomethylpropanesulfonic acids, alkali metal salts thereof, andcombinations thereof; the first anionic monomer is present in an amountin a range of about 1 mol. % to about 3 mol. % of total PVOH polymersand PVOH copolymers in the film; the first PVOH copolymer is present inan amount in a range from about 30 wt. % to about 70 wt. % of total PVOHpolymers and PVOH copolymers in the film; the second PVOH polymer has a4% solution viscosity value at 20° C. in a range of about 20 cP to about30 cP; and the second PVOH polymer is present in an amount in a rangefrom about 30 wt. % to about 70 wt. % of total PVOH polymers and PVOHcopolymers in the film.

33. The water-soluble film of any of paragraphs 24 to 32, wherein thewater-soluble film has a residue value of about 48 wt. % or less asmeasured by the Dissolution Chamber Test.

34. The water-soluble film of any of paragraphs 24 to 33, wherein thewater-soluble film has an average tensile strength value of at leastabout 33 MPa as measured by the Tensile Strength Test.

35. The water-soluble film of any of paragraphs 24 to 34, wherein thewater-soluble film has a modulus value of at least about 12 N/mm² asmeasured by the Modulus Test.

36. An article comprising: a water-soluble film of any of the precedingparagraphs in the form of a pouch defining an interior pouch volume.

37. The article of paragraph 24, further comprising a compositioncontained in the interior pouch volume.

38. An article comprising: a water-soluble film of any of the precedingparagraphs and a household care composition proximal to the film.

1A. An article comprising a water-soluble film and a household carecomposition proximal to the film, where the film comprises: a polyvinylalcohol (PVOH) resin blend comprising: a first PVOH copolymer comprisingan anionic monomer unit, the first PVOH copolymer having a first 4%solution viscosity at 20° C. (μ₁); and a second PVOH polymer consistingessentially of vinyl alcohol monomer units and optionally vinyl acetatemonomer units, the second PVOH polymer having a second 4% solutionviscosity at 20° C. (μ₂); wherein: an absolute viscosity difference|μ₂−μ₁| for the first PVOH copolymer and the second PVOH polymer is in arange of 0 cP to about 10 cP, and the first PVOH copolymer is present inan amount in a range of about 30 wt. % to about 90 wt. % of total PVOHpolymers and PVOH copolymers in the film.

2A. The article of paragraph 1A, wherein the second PVOH polymer ispresent in an amount in a range of about 10 wt. % to about 70 wt. % oftotal PVOH polymers and PVOH copolymers in the film.

3A. The article of any of paragraphs 1A or 2A, wherein the anionicmonomer unit is present in the film in an amount in a range of about 1.0mol. % to about 4.2 mol. % of total PVOH polymers and PVOH copolymers inthe film.

4A. An article comprising a water-soluble film and a household carecomposition, where the film comprises: a polyvinyl alcohol (PVOH) resinblend comprising: a first PVOH copolymer comprising an anionic monomerunit, the first PVOH copolymer having a first 4% solution viscosity at20° C. (μ₁); and a second PVOH polymer consisting essentially of vinylalcohol monomer units and optionally vinyl acetate monomer units, thesecond PVOH polymer having a second 4% solution viscosity at 20° C.(μ₂); wherein: an absolute viscosity difference |μ₂−μ₁| for the firstPVOH copolymer and the second PVOH polymer is in a range of 0 cP toabout 10 cP, and the anionic monomer unit is present in the film in anamount in a range of about 1.0 mol. % to about 4.2 mol. % of total PVOHpolymers and PVOH copolymers in the film.

5A. The article of any of the preceding paragraphs, wherein the anionicmonomer is selected from the group consisting of vinyl acetic acid,maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate,dimethyl maleate, maleic anyhydride, fumaric acid, monoalkyl fumarate,dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaricanyhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate,itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylenesulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts of the foregoing, esters of the foregoing, andcombinations thereof.

6A. The article of any of the preceding paragraphs, wherein the anionicmonomer is selected from the group consisting of acrylamidomethylpropanesulfonic acids, alkali metal salts thereof, andcombinations thereof.

7A. The article of any of the preceding paragraphs, wherein the anionicmonomer is selected from the group consisting of monomethyl maleate,alkali metal salts thereof, and combinations thereof.

8A. The article of any of the preceding paragraphs, wherein the anionicmonomer unit is present in first PVOH copolymer in an amount in a rangeof about 2 mol. % to about 10 mol. %.

9A. The article of paragraph 8A, wherein the anionic monomer unit ispresent in first PVOH copolymer in an amount in a range of about 5 mol.% to about 10 mol. %.

10A. The article of paragraph 9A, wherein the anionic monomer unit ispresent in an amount in a range of about 3 mol. % to about 4.2 mol. % oftotal PVOH polymers and PVOH copolymers in the film.

11A. The article of any of the preceding paragraphs, wherein the PVOHresin blend consists essentially of the first PVOH copolymer and thesecond PVOH polymer.

12A. The article of any of the preceding paragraphs, wherein a viscositydifference (μ₂−μ₁) for the first PVOH copolymer and the second PVOHpolymer is in a range from about 0 cP to about 10 cP.

13A. The article of any of the preceding paragraphs, wherein the firstviscosity μ₁ is in a range of about 4 cP to about 24 cP.

14A. The article of any of the preceding paragraphs, wherein the secondviscosity μ₂ is in a range of about 4 cP to about 24 cP.

15A. The article of any of the preceding paragraphs, wherein thewater-soluble film has a residue value of about 45 wt. % or less asmeasured by the Dissolution Chamber Test.

16A. The article of any of the preceding paragraphs, wherein the firstPVOH copolymer and the second PVOH polymer each independently have adegree of hydrolysis in a range of about 75% to about 99%.

17A. The article of any of the preceding paragraphs, wherein the PVOHresin blend comprises a third PVOH polymer.

18A. The article of any of the preceding paragraphs, wherein thewater-soluble film further comprises at least a third water-solublepolymer which is other than a PVOH polymer.

19A. The article of paragraph 18A, wherein the water-soluble polymer isselected from the group consisting of polyethyleneimines, polyvinylpyrrolidones, polyalkylene oxides, polyacrylamides, cellulose ethers,cellulose esters, cellulose amides, polyvinyl acetates, polyamides,gelatines, methylcelluloses, carboxymethylcelluloses and salts thereof,dextrins, ethylcelluloses, hydroxyethyl celluloses, hydroxypropylmethylcelluloses, maltodextrins, starches, modified starches, guar gum,gum Acacia, xanthan gum, carrageenan, polyacrylates and salts thereof,copolymers thereof, blends thereof, and combinations thereof.

20A. The article of any of the preceding paragraphs, wherein thewater-soluble film further comprises one or more components selectedfrom the group consisting of plasticizers, plasticizer compatibilizers,lubricants, release agents, fillers, extenders, cross-linking agents,antiblocking agents, antioxidants, detackifying agents, antifoams,nanoparticles, bleaching agents, surfactants, and combinations thereof.

21A. The water-soluble film of any of the preceding paragraphs, whereinthe water-soluble film further comprises one or more plasticizers in anamount in a range of about 1 wt. % to about 40 wt. % of the film.

22A. An article comprising water-soluble film and a household carecomposition proximal to the film, where the film comprises: a polyvinylalcohol (PVOH) resin blend comprising: a first PVOH copolymer comprisingan anionic monomer unit, the first PVOH copolymer having a first 4%solution viscosity at 20° C. (μ₁); and a second PVOH polymer consistingessentially of vinyl alcohol monomer units and optionally vinyl acetatemonomer units, the second PVOH polymer having a second 4% solutionviscosity at 20° C. (μ₂) of about 20 cP or less; wherein: the first PVOHcopolymer is present in an amount in a range of about 30 wt. % to about90 wt. % of total PVOH polymers and copolymers in the film (e.g., wherethe water-soluble film or component thereof can incorporate any of therefinements from the preceding paragraphs).

23A. An article comprising water-soluble film and a household carecomposition proximal to the film, where the film comprises: a polyvinylalcohol (PVOH) resin blend comprising: a first PVOH copolymer comprisingan anionic monomer unit, the first PVOH copolymer having a first 4%solution viscosity at 20° C. (μ₁); and a second PVOH polymer consistingessentially of vinyl alcohol monomer units and optionally vinyl acetatemonomer units, the second PVOH polymer having a second 4% solutionviscosity at 20° C. (μ₂) of about 20 cP or less; wherein: the anionicmonomer unit is present in the film in an amount in a range of about 1.2mol. % to about 4.2 mol. % of total PVOH polymers and PVOH copolymers inthe film (e.g., where the water-soluble film or component thereof canincorporate any of the refinements from the preceding paragraphs).

24A. An article comprising water-soluble film and a household carecomposition proximal to the film, where the film comprises: a polyvinylalcohol (PVOH) resin blend comprising: a first PVOH copolymer comprisinga first anionic monomer unit; and a second PVOH polymer consistingessentially of vinyl alcohol monomer units and optionally vinyl acetatemonomer units; wherein the first PVOH copolymer is present in an amountin a range of about 30 wt. % to about 70 wt. % of total PVOH polymersand PVOH copolymers in the film.

25A. The article of paragraph 24A, wherein the second PVOH polymer ispresent in an amount in a range of about 30 wt. % to about 70 wt. % oftotal PVOH polymers and PVOH copolymers in the film.

26A. The article of paragraph 24A or 25A, wherein the first anionicmonomer is selected from the group consisting of vinyl acetic acid,maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate,dimethyl maleate, maleic anyhydride, fumaric acid, monoalkyl fumarate,dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaricanyhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate,itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylenesulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts of the foregoing, esters of the foregoing, andcombinations thereof.

27A. The article of any of paragraphs 24A to 26A, wherein the firstanionic monomer is selected from the group consisting of acrylamidomethylpropanesulfonic acids, alkali metal salts thereof, andcombinations thereof.

28A. The article of any of paragraphs 24A to 27A, wherein the firstanionic monomer is present in an amount less than about 3 mol. % oftotal PVOH polymers and PVOH copolymers in the film.

29A. The article of any of paragraphs 24A to 28A, wherein the first PVOHcopolymer and the second PVOH polymer have 4% solution viscosity valuesat 20° C. that are within about 10 cP of each other.

30A. The article of any of paragraphs 24A to 29A, wherein the first PVOHcopolymer and the second PVOH polymer have 4% solution viscosity valuesat 20° C. that are more than about 10 cP apart from each other.

31A. The article of any of paragraphs 24A to 30A, wherein: the firstPVOH copolymer has a level of incorporation of the first anionic monomerunit in a range of about 3 mol. % to about 5 mol. %; the first anionicmonomer is selected from the group consisting of acrylamidomethylpropanesulfonic acids, alkali metal salts thereof, andcombinations thereof; the first anionic monomer is present in an amountin a range of about 1 mol. % to about 3 mol. % of total PVOH polymersand PVOH copolymers in the film; the first PVOH copolymer is present inan amount in a range from about 40 wt. % to about 60 wt. % of total PVOHpolymers and PVOH copolymers in the film; the second PVOH polymer has a4% solution viscosity value at 20° C. in a range of about 8 cP to about16 cP; and the second PVOH polymer is present in an amount in a rangefrom about 40 wt. % to about 60 wt. % of total PVOH polymers and PVOHcopolymers in the film.

32A. The article of any of paragraphs 24A to 30A, wherein: the firstPVOH copolymer has a level of incorporation of the first anionic monomerunit in a range of about 3 mol. % to about 5 mol. %; the first anionicmonomer is selected from the group consisting of acrylamidomethylpropanesulfonic acids, alkali metal salts thereof, andcombinations thereof; the first anionic monomer is present in an amountin a range of about 1 mol. % to about 3 mol. % of total PVOH polymersand PVOH copolymers in the film; the first PVOH copolymer is present inan amount in a range from about 30 wt. % to about 70 wt. % of total PVOHpolymers and PVOH copolymers in the film; the second PVOH polymer has a4% solution viscosity value at 20° C. in a range of about 20 cP to about30 cP; and the second PVOH polymer is present in an amount in a rangefrom about 30 wt. % to about 70 wt. % of total PVOH polymers and PVOHcopolymers in the film.

33A. The article of any of paragraphs 24A to 32A, wherein thewater-soluble film has a residue value of about 48 wt. % or less asmeasured by the Dissolution Chamber Test.

34A. The article of any of paragraphs 24A to 33A, wherein thewater-soluble film has an average tensile strength value of at leastabout 33 MPa as measured by the Tensile Strength Test.

35A. The article of any of paragraphs 24A to 34A, wherein thewater-soluble film has a modulus value of at least about 12 N/mm² asmeasured by the Modulus Test.

36A. The article of any of paragraphs 1A-35A, wherein the household carecomposition is in contact with the film.

37A. An article of any of paragraphs 1A-36A, wherein the article is inthe form of a pouch comprising at least one sealed compartment.

38A. The article of paragraph 37A, wherein the at least one compartmentcomprises at least one wall, wherein the at least one wall comprises thewater-soluble film.

39A. The article of paragraph 37A-38A, wherein the pouch comprises atleast two compartments.

40A. The article of paragraph 39A, wherein a second compartment issuperposed on a first compartment.

41A. The article of paragraph 37A, wherein the pouch comprises at leastthree compartments.

42A. The article of paragraph 41A, wherein a second compartment and athird compartment are superposed on a first compartment.

43A. The article of any of paragraphs 37A-42A, where the householdcomposition is contained in the at least one compartment.

44A. An article of any of paragraphs 1A-43A, wherein the household carecomposition is selected from the group consisting of light duty liquiddetergents compositions, heavy duty liquid detergent compositions, hardsurface cleaning compositions, detergent gels commonly used for laundry,bleaching compositions, laundry additives, fabric enhancer compositions,shampoos, body washes, other personal care compositions, and mixturesthereof.

45A. The article of any of paragraphs 1A-44A, wherein the compositioncomprises surfactant.

46A. The article of any of paragraphs 1A-45A, wherein the composition isin the form of a liquid, solid, a powder, or mixtures thereof.

47A. A method of forming an article of any of the preceding paragraphs,where the method includes the steps of: providing the film, where thefilm defines an interior pouch container volume; filling the containervolume with a household care composition; and sealing the film to form asealed compartment, where the sealed compartment contains thecomposition.

48A. A method of treating a substrate, where the method includes thestep of contacting the substrate with the article of any of paragraphs1A-46A, or compositions contained therein, typically in the presence ofwater.

Dissolution Chamber Residue Test

A water-soluble film characterized by or to be tested for undissolvedresidue according to the Dissolution Chamber (DC) Test is analyzed asfollows using the following materials:

1. Beaker (4000 ml);

2. Stainless steel washers (3.5″ (88.9 mm) OD, 1.875″ ID (47.6 mm),0.125″ (3.18 mm) thick);

3. Styrene-butadiene rubber gaskets (3.375″ (85.7 mm) OD, 1.91″ ID (48.5mm), 0.125″ thick (3.18 mm));

4. Stainless steel screens (3.0″ (76.2 mm) OD, 200×200 mesh, 0.0021″(0.053 mm) wire OD, 304SS stainless steel wire cloth);

5. Thermometer (0° C. to 100° C., accurate to +/−1° C.);

6. Cutting punch (1.5″ (38.1 mm) diameter);

7. Timer (accurate to the nearest second);

8. Reverse osmosis (RO) water;

9. Binder clips (size #5 or equivalent);

10. Aluminum pans (2.0″ (50.8 mm) OD); and

11. Sonicator.

For each film to be tested, three test specimens are cut from a selectedtest film having a thickness of 3.0±0.10 mil (or 76.2±2.5 μm) using thecutting punch. If cut from a film web, the specimens should be cut fromareas of web evenly spaced along the transverse direction of the web.Each test specimens is then analyzed using the following procedure:

1. Weigh the film specimen and track the specimen through the test.Record the initial film weight (F_(o)).

2. Weigh a set of two sonicated, clean, and dry screens for eachspecimen and track them through the test. Record the initial screenweights (collectively S_(o) for the two screens combined).

3. Assemble a specimen dissolution chamber by flatly sandwiching thefilm specimen between the center of the two screens, followed by the tworubber gaskets (one gasket on each side between the screen and washer),and then the two washers.

4. Secure the dissolution chamber assembly with four binder clips evenlyspaced around the washers and the clips folded back.

5. Fill the beaker with 1,500 ml of reverse osmosis water at laboratoryroom temperature (72+/−3° F., 22+/−2° C.) and record the roomtemperature.

6. Set the timer to a prescribed immersion time of 5 minutes.

7. Place the dissolution chamber assembly into the beaker andimmediately start the timer, inserting the dissolution chamber assemblyat an approximate 45 degree entry angle into the water surface. Thisentry angle helps remove air bubbles from the chamber. The dissolutionchamber assembly rests on the beaker bottom such that the test specimenfilm is positioned horizontally about 10 mm from the bottom. The fourfolded-back binder clips of the dissolution chamber assembly aresuitable to maintain the about 10 mm film clearance from the beakerbottom, however, any other equivalent support means may be used.

8. At the prescribed elapsed prescribed immersion time of 5 minutes,slowly remove the dissolution chamber assembly from the beaker at anapproximate 45 degree angle.

9. Hold the dissolution chamber assembly horizontally over the aluminumpan to catch any drips from the screens and carefully remove the binderclips, washers, and gaskets. Do not break open the sandwiched screens.

10. Place the sandwiched screens (i.e., screen/residual undissolvedfilm/screen) over the aluminum pan and into an oven at 100° C. for 30minutes to dry.

11. Weigh the dried set of sandwiched screens including any residualundissolved film therein. Measure and add to this dried screen weightany dried film drippings captured in and recovered from (e.g., byscraping) the pan when the dissolution chamber assembly was firstremoved from the beaker and during drying. Record the final sandwichedscreen weight (collectively S_(f), including the dried film drippings).

12. Calculate % residue (“DC residue”) left for the film specimen: % DCresidue=100*((S_(f)−S_(o))/F_(o)).

13. Clean the sandwiched screens by soaking them in a beaker of RO waterfor about 20 minutes. Then, take them apart and do a final rinse in thesonicator (turned on and filled with RO water) for at least 5 minutes oruntil no residue is visible on the screens.

Suitable behavior of water-soluble films according to the disclosure ismarked by DC residue values of about 45 wt. % or less or about 48 wt. %or less as measured by the DC Test. In various embodiments, thewater-soluble film has a DC value of at least 1, 2, 5, 10, or 20 wt. %and/or up to about 15, 20, 30, 40, 45 wt. %, or 48 wt. % (e.g., about 5wt. % to about 48 wt. %, about 10 wt. % to about 45 wt. %, about 20 wt.% to about 45 wt. %, or about 30 wt. % to about 40 wt. %).

Tensile Strength Test and Modulus Test

A water-soluble film characterized by or to be tested for tensilestrength according to the Tensile Strength (TS) Test and modulus (ortensile stress) according to the Modulus (MOD) Test is analyzed asfollows. The procedure includes the determination of tensile strengthand the determination of modulus at 100% elongation according to ASTM D882 (“Standard Test Method for Tensile Properties of Thin PlasticSheeting”) or equivalent. An INSTRON tensile testing apparatus (Model5544 Tensile Tester or equivalent) is used for the collection of filmdata. A minimum of three test specimens, each cut with reliable cuttingtools to ensure dimensional stability and reproducibility, are tested inthe machine direction (MD) (where applicable) for each measurement.Tests are conducted in the standard laboratory atmosphere of 23±2.0° C.and 35±5% relative humidity. For tensile strength or modulusdetermination, 1″-wide (2.54 cm) samples of a single film sheet having athickness of 3.0±0.15 mil (or 76.2±3.8 μm) are prepared. The sample isthen transferred to the INSTRON tensile testing machine to proceed withtesting while minimizing exposure in the 35% relative humidityenvironment. The tensile testing machine is prepared according tomanufacturer instructions, equipped with a 500 N load cell, andcalibrated. The correct grips and faces are fitted (INSTRON grips havingmodel number 2702-032 faces, which are rubber coated and 25 mm wide, orequivalent). The samples are mounted into the tensile testing machine,elongated, and analyzed to determine the 100% modulus (i.e., stressrequired to achieve 100% film elongation) and tensile strength (i.e.,stress required to break film).

Optionally, the films can be characterized by particular mechanicalproperties which make the films suitable for processing into articles,e.g. filmed packets.

The water-soluble films according to the disclosure can be marked by TSvalues of at least about 24 MPa or about 28 MPa as measured by the TSTest. Generally, higher TS values are desirable because they correspondto stronger pouch seals when the film is the limiting or weakest elementof a seal. In various embodiments, the water-soluble film has a TS valueof at least about 24, 26, 28, 30, 33, or 35 MPa and/or up to about 32,34, 40, 45, or 50 MPa (e.g., about 24 MPa to about 36 MPa or about 28MPa to about 32 MPa). Alternatively or additionally, an upper bound fora suitable TS value range can be a TS value for a correspondingwater-soluble film having only a single PVOH polymer or PVOH copolymerof the PVOH polymers and PVOH copolymers in the PVOH resin blend (e.g.,a corresponding single-resin film having the higher TS value).

The water-soluble films according to the disclosure can be marked by MODvalues of at least about 11 N/mm² or about 12 N/mm² as measured by theMOD Test. Generally, higher MOD values are desirable because theycorrespond to pouches having a greater stiffness and a lower likelihoodof deforming and sticking to each other when loaded on top of each otherduring production or in final consumer packaging. In variousembodiments, the water-soluble film has a MOD value of at least about11, 12, or 13 N/mm² and/or up to about 13, 14, 15, or 16 N/mm² (e.g.,about 11 N/mm² to about 15 N/mm² or about 12 N/mm² to about 14 N/mm²).Alternatively or additionally, an upper bound for a suitable MOD valuerange can be a MOD value for a corresponding water-soluble film havingonly a single PVOH polymer or PVOH copolymer of the PVOH polymers andPVOH copolymers in the PVOH resin blend (e.g., a correspondingsingle-resin film having the higher MOD value).

EXAMPLES Examples 1-5: Single-Resin Films

Examples 1-5 represent water-soluble films which were formed, eachincluding a single PVOH polymer or PVOH copolymer Resin A-E,respectively. Resins A and B were partially hydrolyzed PVOH polymerswithout anionic comonomers and having different 4% solution viscosities.Resin C was a partially hydrolyzed PVOH copolymer including a 1.82 mol.% level of incorporation of an anionic monomethyl maleate (sodium salt)comonomer (i.e., Resin C was a PVOH terpolymer with vinyl alcohol, vinylacetate, and monomethyl maleate (sodium salt) monomer units). Resins Dand E were partially hydrolyzed PVOH copolymers including 1.77 mol. %and 3.70 mol. % levels of incorporation, respectively, of an anionic2-acrylamido-2-methylpropanesulfonic acid (sodium salt) comonomer (i.e.,Resins D and E were PVOH terpolymers with vinyl alcohol, vinyl acetate,and 2-acrylamido-2-methylpropanesulfonic acid (sodium salt) monomerunits). The films included (i) their respective resins (100 weight partsper hundred resin weight parts (phr)), (ii) glycerol plasticizer (about20-22 phr), (iii) propylene glycol plasticizer (about 10-12 phr), (iv)sorbitol plasticizer (about 5-6 phr), (v) a modified starch filler(about 2-4 phr), (vi) surfactants and other process aids (about 5-7phr), and (vii) residual water (about 9-10 phr). Aqueous compositions ofthe foregoing were cast to form 3.0±0.15 mil (or 76.2±3.8 μm) filmsamples, which were tested for their DC residue values by the abovemethod. Table 1 summarizes the resin and film properties for Examples1-5. In Table 1, the anionic comonomer (AC) content for the films isprovided on a molar basis relative to all of the polymeric resin in thefilm (i.e., excluding the plasticizers and the other non-resincomponents thereof).

TABLE 1 Resin and Film Data for Examples 1-5 Resin Film Example Type μ(cP) DH (%) AC (mol. %) DC (%) AC (mol. %) 1 A 12.5 86 0.00 60.2 0.00 2B 23.5 87 0.00 60.6 0.00 3 C 23.5 92 1.82 49.5 1.82 4 D 24.3 88 1.7749.0 1.77 5 E 12.0 99 3.70 5.8 3.70

FIG. 2 presents the data from Table 1, illustrating the DC residue (wt.%) as a function of AC content (mol. %) of the PVOH (co)polymer resinforming the film. As shown, the DC residue is highly correlated with theAC content. The curved, convex shape of the DC residue (y) vs. ACcontext (x) relationship is illustrated in FIG. 2 with a quadratic curve(y(x)=−4.491x²+1.864x+60.38; r²=0.9996) for the films tested.

Examples 6-10: Two-Resin Blend Films

Examples 6-10 represent water-soluble films which were formed, eachincluding a blend of two of the PVOH polymer or PVOH copolymer ResinsA-E. Specific blends included PVOH Resins A and E (Example 6), A and C(Example 7), A and D (Example 8), B and E (Example 9), and A and B(Example 10). The blend films included 100 phr combined of the tworesins forming a given blend in a range of relative weight proportionsas set forth in Tables 2-6 below, while plasticizers and other additiveswere present in the amounts and types as described for Examples 1-5.Aqueous compositions of the foregoing blend film compositions were castto form 3.0±0.15 mil (or 76.2±3.8 μm) film samples, which were testedfor their DC residue values, TS values, and MOD values by the abovemethods. Tables 2-6 summarize the resin and film properties for Examples6-10. The first and last entries for each of Tables 2-6 represent thesingle-resin limit for the film formulation, while the remaining valuesrepresent the two-resin blend formulations In Tables 2-6, the anioniccomonomer (AC) content for the films is provided on a molar basisrelative to all of the polymeric resin in the film (i.e., including bothresins present but excluding the plasticizers and the other non-resincomponents thereof).

TABLE 2 Resin and Film Data for Example 6 (A/E Blend) Film Resins MOD ACAmt. Amt. DC TS (N/ (mol. Example Type (phr) Type (phr) (%) (MPa) mm²)%) 6 A 0 E 100 7.82 30.47 13.12 3.70 A 5 E 95 9.50 28.64 11.94 3.51 A 10E 90 6.38 24.24 11.01 3.32 A 20 E 80 17.73 35.11 11.86 2.95 A 30 E 7011.31 30.38 11.19 2.58 A 40 E 60 21.22 29.63 12.88 2.20 A 45 E 55 39.0528.76 12.15 2.02 A 50 E 50 36.15 30.57 12.76 1.83 A 55 E 45 42.32 31.8314.46 1.65 A 60 E 40 44.52 29.74 14.65 1.46 A 70 E 30 48.66 35.79 13.771.10 A 80 E 20 59.72 35.31 12.91 0.73 A 90 E 10 62.18 34.61 11.90 0.36 A100 E 0 60.20 32.91 10.82 0.00

TABLE 3 Resin and Film Data for Example 7 (A/C Blend) Film Resins MOD ACAmt. Amt. DC TS (N/ (mol. Example Type (phr) Type (phr) (%) (MPa) mm²)%) 7 A 0 C 100 50.08 34.43 13.27 1.82 A 30 C 70 53.59 32.49 12.73 1.28 A40 C 60 60.41 34.10 15.72 1.10 A 45 C 55 58.23 32.19 14.03 1.01 A 50 C50 58.36 28.70 13.09 0.91 A 55 C 45 54.85 32.19 15.17 0.82 A 60 C 4061.39 26.80 12.61 0.73 A 70 C 30 56.58 26.79 12.33 0.55 A 80 C 20 63.0431.21 14.99 0.37 A 90 C 10 61.40 30.27 12.07 0.18 A 100 C 0 60.20 32.9110.82 0.00

TABLE 4 Resin and Film Data for Example 8 (A/D Blend) Film Resins MOD ACAmt. Amt. DC TS (N/ (mol. Example Type (phr) Type (phr) (%) (MPa) mm²)%) 8 A 0 D 100 49.02 38.88 11.50 1.77 A 10 D 90 52.24 40.27 11.51 1.59 A20 D 80 46.92 38.98 7.81 1.40 A 30 D 70 56.20 35.65 10.46 1.22 A 40 D 6057.24 40.68 12.01 1.04 A 50 D 50 55.76 38.68 12.23 0.87 A 60 D 40 62.3637.03 11.11 0.69 A 70 D 30 61.24 38.84 12.34 0.52 A 80 D 20 65.05 35.2811.62 0.34 A 90 D 10 63.08 33.69 10.68 0.17 A 100 D 0 60.20 32.91 10.820.00

TABLE 5 Resin and Film Data for Example 9 (B/E Blend) Film Resins MOD ACAmt. Amt. DC TS (N/ (mol. Example Type (phr) Type (phr) (%) (MPa) mm²)%) 9 B 0 E 100 5.78 28.48 12.66 3.70 B 10 E 90 10.86 27.86 11.57 3.32 B20 E 80 27.34 28.87 12.23 2.94 B 30 E 70 36.53 35.80 12.52 2.57 B 40 E60 40.61 34.04 11.71 2.20 B 50 E 50 46.35 33.05 12.66 1.82 B 60 E 4052.67 29.22 14.34 1.46 B 70 E 30 46.58 39.69 11.83 1.09 B 80 E 20 62.6527.40 10.20 0.72 B 90 E 10 59.69 31.30 11.25 0.36 B 100 E 0 60.57 33.4412.04 0.00

TABLE 6 Resin and Film Data for Example 10 (A/B Blend) Film Resins MODAC Amt. Amt. DC TS (N/ (mol. Example Type (phr) Type (phr) (%) (MPa)mm²) %) 10 A 100 B 0 60.20 32.91 10.82 0.00 A 90 B 10 58.33 35.04 12.550.00 A 80 B 20 62.96 30.26 9.53 0.00 A 70 B 30 56.41 35.85 13.94 0.00 A60 B 40 61.34 36.23 12.41 0.00 A 50 B 50 60.08 36.14 10.37 0.00 A 40 B60 65.02 38.17 12.99 0.00 A 30 B 70 57.22 38.29 12.71 0.00 A 20 B 8065.17 36.89 13.26 0.00 A 10 B 90 65.77 39.21 12.36 0.00 A 0 B 100 60.5733.44 12.04 0.00

FIGS. 3 and 4 present the data from Tables 2-6, illustrating the DCresidue (wt. %) as a function of AC content (mol. %) of the PVOH(co)polymer resin blend forming the film. As seen in FIG. 3, the DCresidue data for Examples 7-10 generally follow the same curved, convexshape of the DC residue vs. AC content relationship illustrated in FIG.2 for the single-polymer resin films of Examples 1-5. Relative to boththe single-polymer resin films of Examples 1-5 and the two-polymer resinblend films of Examples 7-10, however, the two-polymer resin blend filmsof Example 6 (A/E blend) exhibit a substantially improved reduction inDC residue over wide range of blend compositions. Specifically, the A/Eblend films of Example 6 demonstrate substantially reduced DC residue atAC contents ranging from about 1 mol. % to about 3.4 mol. %, especiallyfrom about 1.4 mol. % to about 2.6 mol. %. The corresponding blendcompositions for the favorable films of Example 6 include about 30 wt. %to about 90 wt. % Resin E (especially about 40 wt. % to about 70 wt. %Resin E) and about 10 wt. % to about 70 wt. % Resin A (especially about30 wt. % to about 60 wt. % Resin A).

FIG. 4, which illustrates a subset of the data in FIG. 3, provides acomparison of Example 6 (A/E blend) films with Example 9 (B/E blend)films. As seen in the graph, the Example 9 (B/E blend) films do notprovide an improved DC residue performance relative to either thecomparison baseline of Examples 1-5 or Examples 7-10 collectively, eventhough both Examples 6 and 9 span the same range of AC content valuesand both share the same anionic PVOH copolymer Resin E (i.e., both havethe 2-acrylamido-2-methylpropanesulfonic acid (sodium salt) comonomer inthe same amounts). The primary difference between Example 6 and 9 is the4% solution viscosity of the PVOH polymer Resin A in Example 6 (about12.5 cP) compared with that of the PVOH polymer Resin B in Example 9(about 23.5 cP).

Comparisons of other examples similarly illustrate the advantages of theExample 6 (A/E blend) films. The Example 8 (A/D blend) films share thesame PVOH polymer Resin A and the same anionic comonomer as the Example6 (A/E blend) films (i.e., both Resins D and E have the2-acrylamido-2-methylpropanesulfonic acid (sodium salt) comonomer), yetthe Example 8 (A/D blend) films do not provide an improved DC residueperformance relative to the comparison baseline of either Examples 1-5or Examples 7-10 collectively. Accordingly, the presence of2-acrylamido-2-methylpropanesulfonic acid (sodium salt) comonomer alonedoes not necessarily provide improved DC residue performance. TheExample 10 (A/B blend) films, which include two PVOH polymers ofdifferent viscosity (or, equivalently, molecular weight), haverelatively high DC residue values. Accordingly, the relatively lowerviscosity (or molecular weight) of Resin A in the Example 6 (A/E blend)films does not necessarily provide improved DC residue performancealone.

Example 11: Illustrative Compositions

Tables 7-15 show illustrative compositions that may be combined with thearticles described herein. For example, the compositions below, whichare intended to be non-limiting examples, may be encapsulated in thewater-soluble films described herein, for example in a pouch.

A bleach additive can include the ingredients presented in Table 7.

TABLE 7 A Wt. % Sodium Percarbonate 25 Bleach activator¹ 7 SodiumCarbonate 15 Sodium Citrate 10 Zeolite 10 Sodium Sulfate 15 Enzymes 2Optical brighteners 2 Miscellaneous To 100 ¹Tetraacetyl ethylene diamine

Granular laundry detergents can include the ingredients presented inTable 8.

TABLE 8 B C D E F G (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) Linearalkylbenzenesulfonate 8 7.1 7 6.5 7.5 7.5 AE3S 0 4.8 0 5.2 4 4 C12-14Alkylsulfate 1 0 1 0 0 0 AE7 2.2 0 3.2 0 0 0 C₁₀₋₁₂ Dimethyl 0.75 0.940.98 0.98 0 0 hydroxyethylammonium chloride Crystalline layered silicate(d-Na₂Si₂O₅) 4.1 0 4.8 0 0 0 Zeolite A 5 0 5 0 2 2 Citric Acid 3 5 3 42.5 3 Sodium Carbonate 15 20 14 20 23 23 Silicate 2R (SiO₂:Na₂O at ratio2:1) 0.08 0 0.11 0 0 0 Soil release agent 0.75 0.72 0.71 0.72 0 0Acrylic Acid/Maleic Acid Copolymer 1.1 3.7 1.0 3.7 2.6 3.8Carboxymethylcellulose 0.15 1.4 0.2 1.4 1 0.5 Protease - Purafect ® (84mg active/g) 0.2 0.2 0.3 0.15 0.12 0.13 Amylase - Stainzyme Plus ® (20mg active/g) 0.2 0.15 0.2 0.3 0.15 0.15 Lipase - Lipex ® (18.00 mgactive/g) 0.05 0.15 0.1 0 0 0 Amylase - Natalase ® (8.65 mg active/g)0.1 0.2 0 0 0.15 0.15 Cellulase - Celluclean ™ (15.6 mg active/g) 0 0 00 0.1 0.1 TAED 3.6 4.0 3.6 4.0 2.2 1.4 Percarbonate 13 13.2 13 13.2 1614 Na salt of Ethylenediamine-N,N′-disuccinic 0.2 0.2 0.2 0.2 0.2 0.2acid, (S,S) isomer (EDDS) Hydroxyethane di phosphonate (HEDP) 0.2 0.20.2 0.2 0.2 0.2 MgSO₄ 0.42 0.42 0.42 0.42 0.4 0.4 Perfume 0.5 0.6 0.50.6 0.6 0.6 Suds suppressor agglomerate 0.05 0.1 0.05 0.1 0.06 0.05 Soap0.45 0.45 0.45 0.45 0 0 Sulphonated zinc phthalocyanine (active) 0.00070.0012 0.0007 0 0 0 S-ACMC 0.01 0.01 0 0.01 0 0 Direct Violet 9 (active)0 0 0.0001 0.0001 0 0 Sulfate/Water & Miscellaneous Balance to 100

Liquid laundry detergents can include the ingredients presented in Table9.

TABLE 9 H I J K L M Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Glycerol 3 5 6.10.6 5 5.3 1,2 Propanediol 16 14 15.9 12 10 Citric acid 1 1.2 0.5 0.5Isopropanol 7.7 NaOH 0.5 1 Marlipal C₁₂₋₁₄EO₇ 22 11.8 14 20.1 C₁₃₋₁₅EO₉1 15 C₉₋₁₁EO₉ 72 Linear alkyl benzene sulfonic acid¹ 16 25 14.5 23 24.6C₁₂₋₁₈ Fatty acid 16 5 12.5 6 16.4 C₁₂₋₁₄ alkyl ethoxy 3 sulfate 11.1 9Enzymes 2.5 1.5 1.3 2.0 1.5 2.0 Polyethyleneimine ethoxylate PEI 600 25.0 3.0 E20 Diethylenetriamine Pentaacetic Acid 0.9 1 Dequest 2010 1.5 11.1 Optical brightening agent 1 1.2 2.5 0.5 0.2 Mg Cl₂ 0.7 0.2 Potassiumsulfite 0.5 0.35 0.2 Structurant 0.21 0.13 0.15 Silicone softening agent(PDMS) 2.5 Water 8 10 7 6 9 Miscellaneous (dyes, aesthetics, To 100 To100 To 100 To 100 To 100 To 100 perfume etc) Monoethanol amine To pH 7.6To pH 7.5 To pH 7.4 To pH 7.6 To pH 7.6 To pH 7.6 ¹Preferred LAS alsocomprise an alkyl group comprising from about 9 to about 15 carbonatoms, in straight chain configuration.

The detergents can include the formulation presented in Table 10.

TABLE 10 N Wt. % Dimethyl monoethyl ether 73.87 Sodium lauryl sulfate6.00 Dimethyl glyoxime 1.00 Isopropyl alcohol 0.5 Triazine stilbene(Tinopal UNPA- 0.4 GX) Monoethanol amine 1.52 Linear alcohol ethoxylate13.61 (Surfonic LF-17) d-limonene 3.00

The composition can include the formulation presented in Table 11.

TABLE 11 O P Wt. % Wt. % Cationic Softener Active¹ 65.0 65.0 Fatty Acid²1.8 1.8 TMPD³ 14.7 14.7 Cocoamide 6EO⁴ 4.05 4.05 Perfume 5 2.5 PerfumeMicrocapsules — 1.25 Dye 0.001 0.001 Hexylene Glycol⁶ 5.63 5.6 Ethanol⁶5.63 5.6 ¹Di(acyloxyethyl)(2-hydroxy ethyl) methyl ammonium methylsulfate wherein the acyl group is derived from partially hydrogenatedcanola fatty acid. ²Partially hydrogenated canola fatty acid.³2,2,4-trimethyl-1,3-pentanediol ⁴PEG 6 cocamide-polyethylene glycolamide of coconut fatty acid. ⁵Sodium salt of hydroxyethane diphosphonicacid ⁶Material included with softening active by supplier.

Multi-compartment pouches can contain a plurality of benefit agents. Byway of a non-limiting example, a two- or three-component pouch maycontain the formulations presented in Table 12 in separate enclosures,where dosage is the amount of the formulation in the respectiveenclosure.

TABLE 12 Q R S 3 compartments 2 compartments 3 compartments Compartment# 1 2 3 1 2 1 2 3 Dosage (g) 34.0 3.5 3.5 30.0 5.0 25.0 1.5 4.0Ingredients Weight % Alkylbenzene sulfonic acid 20.0 20.0 20.0 10.0 20.020.0 Alkyl sulfate 2.0 C12-14 alkyl 7-ethoxylate 17.0 17.0 17.0 17.017.0 Cationic surfactant 1.0 Zeolite A 10.0 C12-18 Fatty acid 13.0 13.013.0 18.0 18.0 Sodium acetate 4.0 enzymes 0-3 0-3 0-3 0-3 0-3 SodiumPercarbonate 11.0 TAED 4.0 Organic catalyst ¹ 1.0 PAP granule ² 50Polycarboxylate 1.0 Polyethyleneimine ethoxylate ³ 2.2 2.2 2.2Hydroxyethane diphosphonic acid 0.6 0.6 0.6 0.5 Ethylene diaminetetra(methylene phosphonic) 0.4 acid Brightener 0.2 0.2 0.2 0.3 0.3Mineral oil Hueing dye ⁴ 0.05 0.035 0.12 Perfume 1.7 1.7 0.6 1.5 Waterand minors (antioxidant, aesthetics, . . .) 10.0 10.0 10.0 4.0 Buffers(sodium carbonate, monoethanolamine) ⁵ To pH 8.0 for liquids To RA > 5.0for powders Solvents (1,2 propanediol, ethanol) for liquids, To 100%sodium sulfate for powders ¹ Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2-ethyl-hexyloxymethyl)-ethyl]esteras described in U.S. Pat. No. 7,169,744 ² PAP =Phtaloyl-Amino-Peroxycaproic acid, as a 70% active wet cake ³Polyethylenimine (MW = 600) with 20 ethoxylate groups per —NH. ⁴Ethoxylated thiophene, EO (R₁ + R₂) = 5 ⁵ RA = Reserve Alkalinity (gNaOH/dose)

In another embodiment of multicomponent pouches, the respectiveenclosures can be filled with liquid and solid benefit agents.Non-limiting examples of two compartment pouches, where one enclosure isfilled with a liquid and one is filled with a solid, includecombinations of the formulations presented in Tables 13 and 14.

TABLE 13 T U V W Liquid formulation XL1 XL2 XL3 XL4 dosage 10 g 5 g 15 g7 g Wt % Wt % Wt % Wt % Marlipal C24-7 74 20 14 Non ionic surfactant 55Neodol 23-5 Anionic surfactant¹ 20 20 25 Propane diol 10 4 22 10Glycerol 2 5 5 Soil dispersant² 2 Amphiphili 5 alkoxylated greasecleaning polymer³ Fatty acid 10 20 Enzymes 3 Structurant 3 Perfume 7 10Water 2 3 5 Monoethanol amine To pH 7.5 Minors To 100% ¹Linear C11-13alkyl benzene sulfonic acid²(bis(C₂H₅O)(C₂H₄O)_(n))(CH₃)—N⁺—CxH2x—N⁺—(CH₃)-bis((C₂H₅O)(C₂H₄O)_(n)),wherein n = from 15 to 30, and x = from 3 to 8. ³Random graft copolymeris a polyvinyl acetate grafted polyethylene oxide copolymer having apolyethylene oxide backbone and multiple polyvinyl acetate side chains.The molecular weight of the polyethylene oxide backbone is about 6000and the weight ratio of the polyethylene oxide to polyvinyl acetate isabout 40 to 60 and no more than 1 grafting point per 50 ethylene oxideunits.

TABLE 14 X Y Z AA Powder formulation XP1 XP2 XP3 XP4 Dosage 35 g 25 g 40g 30 g Wt % Wt % Wt % Wt % Anionic surfactant 20 20 20 Cationicsurfactant 1.5 1.5 Bleach agent 20 36 36 36 Chelating agent 0.8 2 2 2Enzyme 10 10 10 Sodium carbonate 6 4 4 Sodium bicarbonate 4 4 Zeolite 4020 15 15 Fluorescent whitening agent 0.5 3 1 Polymers 2 5 5 Sodiumsulfate 15 Minors To 100%

A hard surface cleaning composition, which may be used by professionals,can include the formulation presented in Table 15.

TABLE 15 Ingredient Name WT % C10 alkyl alcohol-8-ethoxylate 55.0 Linearalkylbenzene sulfonic acid 9.0 Monoethanolamine 2.4 1,2 propanediol 9.0Glycerol 7.5 C1218 alkyl fatty acid 2.5 Dye 0.1 Perfume 2.2 WaterBalance

The foregoing description is given for clearness of understanding only,and no unnecessary limitations should be understood therefrom, asmodifications within the scope of the invention may be apparent to thosehaving ordinary skill in the art.

Throughout this specification and the claims which follow, unless thecontext requires otherwise, the word “comprise” and variations such as“comprises” and “comprising” will be understood to imply the inclusionof a stated integer or step or group of integers or steps but not theexclusion of any other integer or step or group of integers or steps.

Throughout the specification, where compositions are described asincluding components or materials, it is contemplated that thecompositions can also consist essentially of, or consist of, anycombination of the recited components or materials, unless describedotherwise. Likewise, where methods are described as including particularsteps, it is contemplated that the methods can also consist essentiallyof, or consist of, any combination of the recited steps, unlessdescribed otherwise. The invention illustratively disclosed hereinsuitably may be practiced in the absence of any element or step which isnot specifically disclosed herein.

The practice of a method disclosed herein, and individual steps thereof,can be performed manually and/or with the aid of or automation providedby electronic equipment. Although processes have been described withreference to particular embodiments, a person of ordinary skill in theart will readily appreciate that other ways of performing the actsassociated with the methods may be used. For example, the order ofvarious of the steps may be changed without departing from the scope orspirit of the method, unless described otherwise. In addition, some ofthe individual steps can be combined, omitted, or further subdividedinto additional steps.

All patents, publications and references cited herein are hereby fullyincorporated by reference. In case of conflict between the presentdisclosure and incorporated patents, publications and references, thepresent disclosure should control.

1.-83. (canceled)
 84. A method of forming an article, wherein the methodcomprises the steps of: providing a water-soluble film, wherein the filmdefines an interior pouch container volume and comprises: a polyvinylalcohol (PVOH) resin blend comprising: a first PVOH copolymer comprisingan anionic monomer unit, the first PVOH copolymer having a first 4%solution viscosity at 20° C. (μ₁); and a second PVOH polymer consistingessentially of vinyl alcohol monomer units and optionally vinyl acetatemonomer units, the second PVOH polymer having a second 4% solutionviscosity at 20° C. (μ₂); wherein: (A) an absolute viscosity difference|μ₂−μ₁| for the first PVOH copolymer and the second PVOH polymer is in arange of 0 cP to about 10 cP, and the first PVOH copolymer is present inan amount in a range of about 30 wt. % to about 90 wt. % of total PVOHpolymers and PVOH copolymers in the film; or (B) an absolute viscositydifference |μ₂−μ₁| for the first PVOH copolymer and the second PVOHpolymer is in a range of 0 cP to about 10 cP, and the anionic monomerunit is present in the film in an amount in a range of about 1.0 mol. %to about 4.2 mol. % of total PVOH polymers and PVOH copolymers in thefilm; or (C) the second viscosity μ₂ is about 20 cP or less, and thefirst PVOH copolymer is present in an amount in a range of about 30 wt.% to about 90 wt. % of total PVOH polymers and copolymers in the film;or (D) the second viscosity μ₂ is about 20 cP or less, and the anionicmonomer unit is present in the film in an amount in a range of about 1.0mol. % to about 4.2 mol. % of total PVOH polymers and PVOH copolymers inthe film; or (E) the first PVOH copolymer is present in an amount in arange of about 30 wt. % to about 70 wt. % of total PVOH polymers andPVOH copolymers in the film; filling the container volume with acomposition, wherein: the composition is selected from the groupconsisting of (b1) a household care composition proximal to the film,wherein the first PVOH copolymer is present in an amount of at least 65wt. % of total PVOH polymers and PVOH copolymers in the film, (b2) acomposition other than a household care composition proximal to thefilm, and (b3) a household care composition proximal to the film,wherein the first PVOH copolymer is present in an amount of less than 65wt. % of total PVOH polymers and PVOH copolymers in the film, and thehousehold care composition is selected from the group consisting ofliquid detergent compositions, hard surface cleaning compositions,laundry detergent gels, bleach and laundry additives, fabric enhancercompositions, shampoos, body washes, and combinations thereof; andsealing the film to form a sealed compartment, wherein the sealedcompartment contains the composition.
 85. (canceled)
 86. The method ofclaim 84, wherein the composition is (b1) the household care compositionproximal to the film, wherein the first PVOH copolymer is present in anamount of at least 65 wt. % of total PVOH polymers and PVOH copolymersin the film.
 87. The method of claim 84, wherein the composition is (b2)the composition other than a household care composition proximal to thefilm.
 88. The method of claim 84, wherein the composition is (b3) thehousehold care composition proximal to the film, wherein the first PVOHcopolymer is present in an amount of less than 65 wt. % of total PVOHpolymers and PVOH copolymers in the film.
 89. The method of claim 84,wherein: (A) the absolute viscosity difference |μ₂−μ₁| for the firstPVOH copolymer and the second PVOH polymer is in a range of 0 cP toabout 10 cP, and the first PVOH copolymer is present in an amount in arange of about 30 wt. % to about 90 wt. % of total PVOH polymers andPVOH copolymers in the film.
 90. The method of claim 84, wherein: (B)the absolute viscosity difference |μ₂−μ₁| for the first PVOH copolymerand the second PVOH polymer is in a range of 0 cP to about 10 cP, andthe anionic monomer unit is present in the film in an amount in a rangeof about 1.0 mol. % to about 4.2 mol. % of total PVOH polymers and PVOHcopolymers in the film.
 91. The method of claim 84, wherein: (C) thesecond viscosity μ₂ is about 20 cP or less, and the first PVOH copolymeris present in an amount in a range of about 30 wt. % to about 90 wt. %of total PVOH polymers and copolymers in the film.
 92. The method ofclaim 84, wherein: (D) the second viscosity μ₂ is about 20 cP or less,and the anionic monomer unit is present in the film in an amount in arange of about 1.0 mol. % to about 4.2 mol. % of total PVOH polymers andPVOH copolymers in the film.
 93. The method of claim 84, wherein: (E)the first PVOH copolymer is present in an amount in a range of about 30wt. % to about 70 wt. % of total PVOH polymers and PVOH copolymers inthe film.
 94. The method of claim 84, wherein the second PVOH polymerconsists of vinyl alcohol monomer units and optionally vinyl acetatemonomer units.
 95. The method of claim 84, wherein the second PVOHpolymer is present in an amount in a range of about 10 wt. % to about 70wt. % of total PVOH polymers and PVOH copolymers in the film.
 96. Themethod of claim 84, wherein the anionic monomer unit is present in thefilm in an amount in a range of about 1.0 mol. % to about 4.2 mol. % oftotal PVOH polymers and PVOH copolymers in the film.
 97. The method ofclaim 84, wherein the anionic monomer is selected from the groupconsisting of vinyl acetic acid, maleic acid, monoalkyl maleate, dialkylmaleate, monomethyl maleate, dimethyl maleate, maleic anyhydride,fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate,dimethyl fumarate, fumaric anyhydride, itaconic acid, monomethylitaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonic acid,allyl sulfonic acid, ethylene sulfonic acid,2-acrylamido-1-methylpropanesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts of the foregoing, esters of the foregoing, andcombinations thereof.
 98. The method of claim 84, wherein the anionicmonomer is selected from the group consisting of acrylamidomethylpropanesulfonic acids, alkali metal salts thereof, andcombinations thereof.
 99. The method of claim 84, wherein the anionicmonomer is selected from the group consisting of monomethyl maleate,alkali metal salts thereof, and combinations thereof.
 100. The method ofclaim 84, wherein the anionic monomer unit is present in first PVOHcopolymer in an amount in a range of about 2 mol. % to about 10 mol. %.101. The method of claim 100, wherein the anionic monomer unit ispresent in first PVOH copolymer in an amount in a range of about 5 mol.% to about 10 mol. %.
 102. The method of claim 101, wherein the anionicmonomer unit is present in an amount in a range of about 3 mol. % toabout 4.2 mol. % of total PVOH polymers and PVOH copolymers in the film.103. The method of claim 84, wherein the PVOH resin blend consistsessentially of the first PVOH copolymer and the second PVOH polymer.104. The method of claim 84, wherein a viscosity difference (μ₂−μ₁) forthe first PVOH copolymer and the second PVOH polymer is in a range fromabout 0 cP to about 10 cP.
 105. The method of claim 84, wherein thefirst viscosity μ₁ is in a range of about 4 cP to about 24 cP.
 106. Themethod of claim 84, wherein the second viscosity μ₂ is in a range ofabout 4 cP to about 24 cP.
 107. The method of claim 84, wherein thewater-soluble film has a residue value of about 45 wt. % or less asmeasured by the Dissolution Chamber Test.
 108. The method of claim 84,wherein the first PVOH copolymer and the second PVOH polymer eachindependently have a degree of hydrolysis in a range of about 75% toabout 99%.
 109. The method of claim 84, wherein the PVOH resin blendcomprises a third PVOH polymer.
 110. The method of claim 84, wherein thewater-soluble film further comprises at least a third water-solublepolymer which is other than a PVOH polymer.
 111. The method of claim 84,wherein the third water-soluble polymer is selected from the groupconsisting of polyethyleneimines, polyvinyl pyrrolidones, polyalkyleneoxides, polyacrylamides, cellulose ethers, cellulose esters, celluloseamides, polyvinyl acetates, polyamides, gelatines, methylcelluloses,carboxymethylcelluloses and salts thereof, dextrins, ethylcelluloses,hydroxyethyl celluloses, hydroxypropyl methylcelluloses, maltodextrins,starches, modified starches, guar gum, gum Acacia, xanthan gum,carrageenan, polyacrylates and salts thereof, copolymers thereof, blendsthereof, and combinations thereof.
 112. The method of claim 84, whereinthe water-soluble film further comprises one or more components selectedfrom the group consisting of plasticizers, plasticizer compatibilizers,lubricants, release agents, fillers, extenders, cross-linking agents,antiblocking agents, antioxidants, detackifying agents, antifoams,nanoparticles, bleaching agents, surfactants, and combinations thereof.113. The method of claim 84, wherein the water-soluble film furthercomprises one or more plasticizers in an amount in a range of about 1wt. % to about 40 wt. % of the film.